Despite his tender years, Ramsey has already been named Welsh skipper by coach Gary Speed and led his country to a notable 2-1 win over England's Euro 2012 Group G rivals Montenegro in Cardiff on Friday.
With Craig Bellamy and David Vaughan suspended, an encounter with Fabio Capello's men looks like being an altogether different experience for Ramsey and his colleagues.
Walcott knows he could make the build-up very uncomfortable for Ramsey. But he has vowed not to open dialogue until the pair meet ahead of kick-off.
"I won't get into his head now. I'll just see him on Tuesday night," said Walcott.
"He is a very lively character, who is a great professional and very strong mentally.
"(Arsenal manager) Arsene Wenger has got belief in him. He has come back after an horrific injury and for a while he didn't quite look the player he was before.
"Now he is starting to get back, which is great for Arsenal and for Wales. I am sure Wales will get a lot more out of him as captain."
With Bellamy missing, Walcott's old Southampton team-mate Gareth Bale now becomes the player England have to watch.
Bale missed the first meeting between the teams last March and Walcott expects the winger to make up for lost time.
"Hopefully Gareth can start showing his form of last year because we want to see the best players in the Premier League," he said.
"I am sure he can be their main threat.
"The limelight hasn't changed him at all. He is good. But he is poor on his phone. He never answers his phone."
Walcott was part of the victorious England side that put three goals past Bulgaria on Friday to take them within four points of reaching next year's finals in Poland and Ukraine.
That would offer some kind of redemption for the summer of 2010, when the 22-year-old had all his bags packed for South Africa, then was stunned to discover he had been left out of Capello's squad.
Walcott described his feelings in a recently-released autobiography, which did not meet with Fabio Capello's approval.
Evidently, the Italian does not hold a grudge, with Walcott revealing the book is part of an attempt to become more assertive.
"Everyone is entitled to their own opinion. I am as well," he said.
"I am growing up. I want to express how I am feeling, what I want, what I want to achieve.
"I want to show people I care. I want to prove a lot of people wrong and reach the top of my game. There is a lot more to come from me."