Chelsea left-back Ashley Cole is set to become the seventh player to make 100 England appearances when Brazil visit Wembley on Wednesday, and Charlton fully expects Rooney - who has 78 caps at the age of 27 - to follow suit.
Charlton, England's record goalscorer with 49 goals in 106 internationals, said in the new book England Centurions: "Wayne Rooney has the potential to reach 100 caps and much more. He is a great talent, an automatic choice when we have a shortage of top international talent."
Cole will follow in the footsteps of Peter Shilton (125), David Beckham (115), Bobby Moore (108), Charlton, Billy Wright (105) and Steven Gerrard (100) in reaching the milestone if he takes the field against Brazil.
Charlton said of the 32-year-old: "Ashley Cole is a good player, and no-one could not be considered top quality to reach 100 caps, and also in top condition because it does demand stamina to play on for so long.
"So I would wish all those reaching 100 caps 'good luck'."