The Three Lions will host the five-time World Cup winners on Wednesday February 6 2013, before entertaining The Boys in Green on Wednesday May 29 2013.
Both games form part of The FA's 150th anniversary year, with the Champions League final staged at Wembley for the second time in three seasons as part of the celebrations.
England will then visit Rio de Janiero later that year in June 2013 as part of a two-game tour of the South American country, who are hosting the 2014 World Cup. The second opponents are yet to be confirmed.
"We're delighted Brazil will kick-off The FA's 150th anniversary celebrations at Wembley. 2013 is a landmark year for The FA and an exciting England fixture programme, in addition to Wembley hosting the UEFA Champions League Final, will form a key part of the celebrations," Club England Managing Director Adrian Bevington told the FA's official website.
"As the most successful footballing nation, with great players and supporters, it will be fantastic to launch this important year in English football's history against such outstanding opponents as Brazil.
"We also look forward to hosting Republic of Ireland and Scotland at Wembley next year. These matches are sure to evoke great passion among supporters.
"We have been planning the fixtures in Brazil for over a year, as a key part of our preparation for 2014 - subject to qualification.
"Our players do not have any experience of playing in South America and it will undoubtedly be beneficial for the team to travel and play in Brazil, a year ahead of the World Cup. We negotiated our qualifying schedule with a specific view to allowing this.
"While in Brazil, The FA and England squad will play an active role in developing and supporting a charity programme both in advance of and during the summer of 2013 and 2014."
