The five-times World Cup winners will face Three Lions at Wembley on February 6 2013, with a match in Rio de Janeiro also slated for early June 2013, with Roy Hodgson's men expected to face a second South American team in a mini-tour.
Meanwhile, Republic of Ireland will play their first game at the new Wembley stadium on May 29 2013.
|20/1||England are 20/1 with William Hill to win World Cup 2014
Adrian Bevington, managing director of Club England told the FA's website: "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.
"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."