The Burnley defender picked up his first cap in a clash with Spain in 2011, and went on to become one of his nation's most important players.
He missed Euro 2012 and the 2014 World Cup through injury, but played at each of the five major tournaments that followed.
Walker played a big part in England's runs to the Euro 2020 and Euro 2024 finals, and was a key player in the 2018 Three Lions side that became just the third to reach the last four of a World Cup.
“I am sad to be making this decision, but I’m also very proud of what I've achieved with England,” Walker said.
“To represent my country at five major tournaments, to get to the finals that we've reached and to be surrounded by this England team, especially the players and the managers that I've had the privilege of working under, has been a great honour.
“But today is the time that comes to an end. It's good for me to have a little bit of closure to my career on the international stage.
"I know all England fans will join me in congratulating Kyle on an incredible international career," said England manager Thomas Tuchel.
"Although I only worked with him for a short period of time, I was always aware that he was one of England’s greats who fully embraced the highest honour of representing his country.
“An international career spanning 14 years and five major tournament is testament to Kyle’s dedication. He can look back on his time with the Three Lions with great pride.”