The two teams of celebrities will meet on 5 June in the sixth Soccer Aid, which raises money for Unicef.
Mourinho will be assisted by Sunderland boss Sam Allardyce, with Soccer Aid co-founder Robbie Williams on board as coach.
"I want to be the first one to win the Soccer Aid trophy for both teams, England and the Rest of the World," said the Portuguese, who coached the Rest of the World to a 4-2 victory in the 2014 event.
"Sam and I will make a very good partnership and it will be a great feeling for Claudio to finally lose a match!
"I hope the organisers can help me now with an English passport!"
Ranieri, who has guided Leicester to the top of the Premier League table and within touching distance of an unlikely title triumph, added: "Soccer Aid is a fantastic event, raising money for an amazing children's charity in Unicef.
"For Soccer Aid's 10th anniversary, it is a great honour that Robbie Williams has asked me to manage the Rest of the World XI and I'm looking forward to helping them defend their title."
Previous Soccer Aid matches were held at Wembley in 2008 and at Old Trafford in 2006, 2010, 2012 and 2014, raising over $31 million in total for Unicef.
One Direction's Louis Tomlinson, pop star Olly Murs and comedians Jack Whitehall and John Bishop are among those signed up to play for England this year, with actor Michael Sheen, chef Gordon Ramsay and Westlife's Nicky Byrne among those set to line up for the Rest of the World.