The two teams of celebrities will meet on June 5 in the sixth Soccer Aid, which raises money for Unicef.
Manchester United target Mourinho will be assisted by Sunderland boss Sam Allardyce, with Soccer Aid co-founder Robbie Williams as a 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 Mourinho, who coached the Rest of the World to a 4-2 victory in 2014.
"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 a title triumph, said: "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 have raised over £17m 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.
Actor Michael Sheen, chef Gordon Ramsay and Westlife's Nicky Byrne will play for the Rest of the World.
(dailystar.co.uk)
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