Tuesday, September 16th
Real Madrid vs Marseille - 20:00 BST
Xabi Alonso's first Champions League game as Real Madrid manager at home to Marseille might look like a favourable one on paper, but it would be unwise to write off a Roberto De Zerbi side with bags of talent.
After a strong end to the season, Marseille finished second in Ligue 1 last season; their best league finish since winning the title in the 2009/10 campaign.
De Zerbi's big struggle last season was getting consistent results, and they have started this season in a similar vein with two 1-0 defeats between 5-3 and 4-1 victories. Those results tell a story of an unpredictable side capable of pulling off a shock but also capable of losing badly.
With experienced players like Pierre-Emile Hojbjerg and Nayef Aguerd, Marseille have a solid core which will be pivotal in their European adventure. However, it is the explosiveness and constant goal threat of Mason Greenwood that gives them that X-factor and will give Alonso genuine cause for concern.
Alonso won't be panicking, though; he has one of the best attackers in world football in his corner.
Kylian Mbappe has begun the season in world-class form with seven goals and three assists for club and country already, bringing his tally for Los Blancos to 48 goals in just 63 games.
Don't bet against him hitting the 50-goal mark with a brace against Marseille. Taking on De Zerbi won't be a simple assignment for Alonso, but after four wins from four in LaLiga and Mbappe firing on all cylinders, the Real coach will be quietly confident.
Wednesday, September 17th
Bayern Munich vs Chelsea - 20:00 BST
A repeat of the iconic 2012 Champions League final is exciting viewing for supporters of these two European giants and neutrals alike. If Wednesday's box office encounter delivers even half of that special night in Munich as Chelsea stunned Bayern in their own backyard, then fans will have been treated.
What adds extra intrigue is the heavy Premier League influence in Vincent Kompany's team, with Harry Kane, Luis Diaz and Michael Olise leading their attack, having all previously starred in England's top flight.
It is a big occasion for Enzo Maresca too, as the Chelsea manager makes his managerial Champions League debut against last season's quarter-finalists.
Despite winning the Conference League before becoming World Champions in the summer, Maresca knows the real test of his project begins this season in Europe's premier competition, and testing themselves against Bayern will be the perfect indicator of how good his young Blues are.
Bayern, meanwhile, will be hoping to back up their imperious start to the Bundesliga season, where they have scored goals for fun, with a convincing win in front of their home supporters.
Liverpool vs Atletico Madrid - 20:00 BST
When these two European heavyweights last met in the group stages in 2021, Liverpool got the better of Diego Simeone's men both times, including a thrilling 3-2 win in Madrid. Those matches in October and November came just a few months after Atletico had sensationally won LaLiga and were at the peak of their powers under the Argentine.
Liverpool, meanwhile, were still on the road to becoming the dominant domestic force they are today, even if Jurgen Klopp had already unlocked the code in Europe. Fast forward to 2025, and on paper, the Premier League holders are in a much stronger position than Atletico Madrid as Simeone's magic appears to be finally wearing off.
However, even though Liverpool have won four from four whilst Atletico languish in mid-table, something isn't quite right at Anfield this season, at least not yet. New signings Florian Wirtz and Milos Kerkez have yet to find their feet, and Mo Salah has been non-existent for large periods of all four Premier League games.
A statement win in front of a highly emotive Anfield crowd would be the perfect way to kick-start a season stuck in neutral. Simeone, though, won't let Atletico Madrid go down without pulling a few punches of their own.
Thursday, September 18th
Newcastle vs Barcelona - 20:00 BST
In what promises to be a thrilling three days of European football, the final evening sees six fascinating ties wrap up Matchday 1. Thursday's standout match comes from St James' Park as Newcastle United return to the Champions League with a belief they can be more competitive than their underwhelming 2023/24 campaign (albeit in a group of death).
Eddie Howe's side have improved since then, and although they have lost their star striker Alexander Isak to Liverpool, Newcastle have a nicely balanced squad with a touch of magic in the middle of the park in Bruno Guimaraes. When you factor in the intensity that Howe's side has become notorious for playing (especially at home), you have the recipe for a potential upset.
Hansi Flick's fantastic Barcelona will have other ideas, however. Last season's Champions League semi-finalists were the great entertainers in Europe in 2024/25 with a brand of attacking football which, alongside Luis Enrique's PSG, looks to have once again revolutionised football.
Barcelona will be without superstar Lamine Yamal on Thursday night, and whilst the tricky winger will be a miss for the visitors, they have more than enough firepower in his absence to take three points back to the Camp Nou.
It is Newcastle's challenge to ensure they keep Barca's superstars quiet and deliver an unforgettable European night for a city that lives and breathes football.
Manchester City vs Napoli - 20:00 BST
The final highlight sees Kevin De Bruyne return to the Etihad as his new club Napoli travels to his former club Manchester City, just a few months after leaving Manchester. De Bruyne returns as a City legend, and the six-time Premier League winner will receive a hero's reception on Thursday night before we get down to business.
De Bruyne has made a brilliant start to life in Naples, scoring two goals in Serie A to help Antonio Conte's side win three games from three at the start of the season. The Scudetto champions have begun where they left off last campaign, with Scott McTominay still central to Napoli's success and new signings De Bruyne and Rasmus Hojlund getting off to goal-scoring starts.
Manchester City remain favourites, however. Even if this is a Pep Guardiola team in a transitional period, the way they brilliantly dispatched Manchester United in the Manchester derby was a timely reminder of their quality.
City play in front of their home support again on Thursday, and if Jeremy Doku, Phil Foden and Erling Haaland are in the same mood as they were on Sunday afternoon, City could prove too hot to handle for Napoli.
The hope for the visitors is that Conte shouldn't make it anywhere near as easy for Guardiola as Ruben Amorim did. His Napoli side will be incredibly well-organised, difficult to break down and possess quality players in transition.
Whichever way the game goes, it promises to be a fascinating tactical battle between two of football's most successful modern coaches.