Mourinho claimed he was on the verge of accepting the job in 2007 after Steve McClaren was sacked following England's failure to qualify for Euro 2008.
But the Portuguese had a last-gasp change of heart and decided to stay in club management.
He told l'Equipe: "I was hours away - I almost signed up for the England national team.
"But at the last minute I began thinking, 'I am going to coach a national side, there will be one match a month and the rest of the time I will be in my office or overseeing matches. And then to have to wait until the summer to compete in a European Championship or a World Cup?' No, it wasn't for me.
"So at the last moment I pulled back, preferring to wait for the right job to come along, a good club, a challenge that could motivate me. That was Inter (Milan).''
The Football Association were quick to respond to Mourinho's comments. "Fabio was our first choice for England manager,'' a spokesman said. "We have made that clear from the outset.''
Mourinho left Chelsea in September 2007, two months before McClaren was dismissed, and took up his role as head coach at Inter in June 2008. After guiding Inter to the Champions League he then left for Real Madrid in the summer of 2010.
"When I left Chelsea, the first month was fantastic. I went to Africa, to Japan, I did tons of things I had not been able to do,'' he added. "The second month was also good, but from the third onwards it was horrible, just awful.''
Mourinho admitted he also came close to taking the Paris St Germain job after leaving Stamford Bridge, but decided against it as he was not convinced by Ligue 1's quality.
Asked why he did not take the PSG post, he said: "I do not know. Perhaps because of the feeling that England, Spain or Italy are more powerful leagues, and we must make the most of the best years of our career by working at the highest level.''