Cole is poised to win his 100th England cap against the Brazilians, 11 years after making his debut.
Walcott said: "It is a fantastic achievement. There are only a few top-class players in that category (who reach 100 caps) and I am sure there will be many more to come.
"He is a difficult player to play against. I learned a lot from him. I got the better of him in the last couple of meetings, which I wind him up about all the time.
"We get on very well. I am only going to learn from the likes of him, Steven and Frank.
"Ashley is massively important. He is so experienced and has won many things. A lot of players look up to him.
"He is a strong character. He can deal with anything. It is all about the game. Nothing fazes him. He is very concentrated."