The Chelsea full-back becomes just the seventh player to reach the milestone in a Three Lions shirt, whilst Chris Smalling is handed a surprise start in the centre of defenceRoy Hodgson has handed Ashley Cole his 100th England cap, with the defender set to start in Wednesday's clash with Brazil at Wembley.
There is also a surprise place in the XI for Manchester United defender Chris Smalling, who has started just one Premier League match in 2013.
Wayne Rooney spearheads the England attack alongside Danny Welbeck and Theo Walcott, while Jack Wilshere makes his first start for the Three Lions since June 2011.
New Brazil boss Luiz Felipe Scolari ends Ronaldinho’s year in international exile by selecting him to start. Dangermen Neymar and Oscar will line-up either side of the 32-year-old attacker, with Luis Fabiano leading the line.
Elsewhere, Chelsea’s David Luiz is picked in the heart of the defence alongside debutant Dante, while Ramires partners Premier League target and Corinthians star Paulinho in midfield.
England: Hart; Johnson, Smalling, Cahill, Cole; Wilshere, Cleverley, Gerrard; Walcott, Rooney, Welbeck.
Subs: Butland, Walker, Baines, Jagielka, Lescott, Milner, Lampard, Osman, Lennon, Oxlade-Chamberlain.
Brazil: Cesar; Alves, Luiz, Dante, Adriano; Ramires, Paulinho; Oscar, Ronaldinho, Neymar; Fabiano.
Subs: Diego Alves, Marcelo, Miranda, Leandro Castan, Filipe Luis, Lucas Moura, Arouca, Fred, Hulk.