Mourinho, who was sacked by Chelsea in December after a Premier League loss to Ranieri's Leicester City, will have Sunderland boss Sam Allardyce in the dugout as his assistant.
"I want to be the first one to win the Soccer Aid trophy for both teams," said Mourinho, who led 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," added the 53-year-old, who has been tipped in the British media to take over at either Manchester United or Paris St Germain.
Meanwhile, Ranieri, who has led Leicester's unexpected title charge this campaign, is looking to inflict another loss for Mourinho.
"It is a great honour that (singer and match organiser) Robbie Williams has asked me to manage the Rest of the World XI and I'm looking forward to helping them defend their title," Ranieri said.
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