The famous Italian constructor withdrew from Le Mans to concentrate on Formula One in 1973 with nine wins in the bag.
Back at the Sarthe circuit after a 50-year absence they swept away the years, planting both of their Hypercar entries on the front of the grid.
Toyota, on a six-timer, had to make do with a share of the second row with Porsche, another constructor back burning the midnight oil and seeking their 20th win.
"The suspense is massive," race organiser Pierre Fillon told AFP.
"We knew Ferrari were quick in qualifying... in all the categories and between all the teams it's extremely tight, we're in for a magnificent race," added Fillon, whose brother Francois is a former French Prime Minister.
Completing the premier category are Peugeot and Cadillac, with the American team's number three car driven by Sebastien Bourdais supplying the drama in Friday's qualifying.
Locally-born Bourdais was on target to post the third best time when his car stopped in flames on the Mulsanne straight.
Since 33 cars set off in the rain for the very first edition on May 26, 1923, Le Mans has gone on to earn an exalted place in motorsport's calendar alongside Formula One's Monaco Grand Prix and the Indy 500.
Only one driver - the late Graham Hill - has succeeded in taking the chequered flag in all three of motor racing's 'triple crown'.
The 24 Hour classic has ignited the imagination of numerous Hollywood A-listers over the years.
Paul Newman famously finished second in 1979 aged 54, Patrick Dempsey raced it four times, Steve McQueen used the 1970 edition to shoot scenes of his film 'Le Mans', and in 2016 Brad Pitt gave the celebrated command 'Gentlemen, start your engines'.
Performing the starting honours for the 91st edition on Saturday is basketball superstar LeBron James.
"There's nothing like seeing and experiencing sports at their highest level," said James.
The NBA's all-time leading scorer added: "It's an honour for me to be part of this historic moment in motorsport and help celebrate the centenary of one of the biggest sporting events in the world."
James will be in good company with 62 cars across all categories set to start, with the Le Mans centenary attracting a record sell-out 300,000 crowd.
