The Portuguese was the FA's top choice to restore order after Steve McClaren's sacking following England's failure to qualify for Euro 2008.
Mourinho, who was out of work at the time after leaving Chelsea by mutual consent, admitted coming close to taking the job before later opting against the move.
Speaking exclusively to Rio Ferdinand's Vibe with Five show, Mourinho lifted the lid on links with the Three Lions and claimed he 'could have' taken charge in the past.
"I refused great working opportunities," Mourinho revealed. "The first one was even very hard to refuse because it was Portugal. I could be their coach in the national team.
"Also yours," he added, which sparked Ferdinand to reply 'no way'.
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"Yeah. I had it there, on the table," Mourinho said, referring to a contract. "I'm still there a little bit. It was in 07-08 when Mr Capello got the job
"I didn't (sign) because the national team job is something that I wouldn't enjoy."
Italian Fabio Capello was later handed the task of leading the Three Lions into a 2010 World Cup qualifying campaign but the appointment turned out to be an underwhelming one.
It brought the curtain down on England's famous golden generation of stars such as Ferdinand, Frank Lampard, Steven Gerrard, Paul Scholes and John Terry.
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The 'Special One' had previously revealed that his wife intervened to stop him from becoming England manager, instead taking the head coach role at Inter Milan where he won the Treble in 2010.
"My wife told me not to take it and she was right," Mourinho told the Guardian in 2014. "Lampard, Terry, Joe Cole, everybody, was saying, 'Come, come, come'. My players said: 'The guys from Manchester United and Liverpool call us and say to us: Tell your boss to come.' I had lots of positive things to push me."
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"I cannot wait two years for a big competition. I cannot be spending two years playing against Kazakhstan and San Marino."
Mourinho will no doubt be linked again to the job if Gareth Southgate steps down from his role after Euro 2024.
And he's a big admirer of Jude Bellingham.
"I don't know the kid I never spoke with the kid but I believe that there is something that separates him from the boys that were born in England, developed in England, playing in England, living in England.
"When he scores and open the arms [in celebration], it shows the character, you know? He is not doing it with arrogance.
"It is just you know, yeah, 'I did it again'. You know, you see the kids it's big, big, big personality.
"I cannot say I wish England [will win the Euros], because I think Portugal can do it and I want Portugal do it. But they can do it. That generation can do it."