Chelsea left-back Cole, 33, has struggled for playing time with his club this season with Spaniard Cesar Azpilicueta having been preferred by Jose Mourinho.
Although he has been involved more towards the end of the campaign, it appears Cole has been supplanted by Everton's Leighton Baines and, most likely, Southampton teenager Luke Shaw.
Cole wrote on his Twitter feed: "I got the call from Roy and agree England team should be about the young players. I think it best I retire from England team now.
"We have a great manager and team and I wish them only success. I will be supporting them like a true fan. Thanks to everyone for everything."
The decision brings an end to a lengthy international career for Cole, who made his England debut against Albania in 2001 and has won 107 caps since.
The full-back positions have been subject of plenty of conjecture ahead of Roy Hodgson's squad announcement on Monday afternoon, with Cole's position in question and worries about the availability of Tottenham right-back Kyle Walker.
Walker is struggling with a pelvic injury and if Hodgson's medical staff fear he will not be 100% fit, it could be Manchester United's Phil Jones - also under an injury cloud - heading to Brazil as a back-up to likely starter Glen Johnson.
Cole's omission suggests Hodgson is happy to take a youthful squad to Brazil and could mean a call for Everton midfielder Ross Barkley, who enjoyed a productive end to the season.
Liverpool winger Raheem Sterling and midfielder Jordan Henderson, Arsenal forward Alex Oxlade-Chamberlain and Southampton winger Adam Lallana - all lacking international experience - are also in contention for the 23-man squad which will be named at 2pm.
Watch live coverage of Roy Hodgson's England squad announcement on Sky Sports News on Monday from 2pm.