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England will kick off their campaign on Sunday at Wembley against Croatia, who knocked the Three Lions out of the World Cup semi-finals in Russia three years ago.
Speaking on talkSPORT as part of his Euro 2020 coverage, Mourinho opened up on his picks for England's starting XI against Croatia.
The 58-year-old Portuguese manager selected Dean Henderson ahead of Jordan Pickford as England's No 1.
Mourinho added that he would partner John Stones alongside Tyrone Mings in the absence of Harry Maguire.
Meanwhile, the Special One would complete the England four-man backline with Ben Chilwell at left-back and Kyle Walker at right-back.
"I think Gareth Southgate has great potential in his hands," Mourinho told talkSPORT.
"I would go with Dean Henderson in goal. Without Harry Maguire, I would go John Stones and Tyrone Mings as the centre-backs.
"Conor Coady is clearly a three defenders defender. The kid from Brighton [Ben White] is a good player but he has just arrived, so it doesn't make any sense to go directly in.
"Mings has good leadership qualities, he's aggressive, good personality. Stones is very fast to deal with space.
"Right-backs you can throw a coin, but I would say Kyle Walker because you need pace, and a little bit of experience, an older guy, he closes the space inside maybe better than Reece James and Kieran Tripper.
"Left-back I would go with Ben Chilwell, I wouldn't think twice. He is intelligent, he covers the space, the diagonals inside very well, he is dangerous in attack, he is good in the air, good on set-pieces."
Mourinho snubbed Luke Shaw for the left-back position, despite the United full-back's stellar season in the Premier League.
However, the former United manager argued that Chilwell has "something more, especially with the ball."
Speaking on Shaw, Mourinho said: "He had a good season and clearly an evolution in terms of emotion, professionalism.
"But Chilwell has something more, especially with the ball, the way he thinks, he is very calm under pressure. I like Chilwell."
Mourinho would partner Declan Rice alongside Kalvin Phillips in midfield, with Jack Grealish out on the left wing ahead of Rashford.
The former Chelsea and Tottenham boss opted for Phil Foden out on the right ahead of Sterling, with Mason Mount deployed as the No 10 for England.
England skipper Harry Kane leads Mourinho's starting XI as the Special One called the Tottenham striker "untouchable."
Mourinho said: "To play with Declan Rice, Jude Bellingham would be perfect but maybe this first game play Kalvin Phillips with Rice.
"Harry Kane is untouchable, Jack Grealish is untouchable and the best position for Grealish is coming from the left. For me, Marcus Rashford can only play there. When he plays on the right, he is completely lost. He is very good on the left attacking spaces.
"But Grealish, for me, is tremendous and what he creates and his personality. He reminds me of Luis Figo. I like him very much.
"Grealish on the left, Mason Mount as the number ten and because I like the wingers to come inside, I would play Phil Foden on the right.
"I would play Foden, Mount and Grealish, that is why I'm saying Phillips and Rice."
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