The match will be Luiz Felipe Scolari's first back in charge following his reappointment in December 2012, and has been arranged as part of the Football Association's 150th anniversary celebrations.
And there will be a number of Brazil players with added motivation to impress as they play their club football in the Premier League.
Chelsea playmaker Oscar told CBF TV: "I hope we start 2013 well. It is a beautiful stadium and will be a beautiful game, but we'll do everything to win it.
"It will be different for those of us who play in England. It's a derby, I hope we have a great game, and that I have a great game too."
Oscar's team-mate at Chelsea, Luiz, added: "I have always wanted to work with Scolari. He is a manager that likes to motivate the players.
"I have missed playing for the national team, because it makes me proud to represent Brazil.
"It's a special game. I haven't had the opportunity to play against England, who have many quality players and some of them are my team-mates too."
Cesar is in contention to start in goal following a string of impressive performances for Queens Park Rangers, having made the move to England from Inter Milan last summer.
He said: "I'm very happy for living all of this [being in the national team] again, especially since it's in the country that I chose to continue my career. It couldn't have been more perfect."