The Chelsea manager, who took Porto to European glory last season, rates the Premier League more highly than the Champions League.
"Only a great team can win the Champions League, but it must be a great team with luck," Mourinho said after the draw for the knockout stage pitted Chelsea against another of the Portuguese manager's former employers, Barcelona.
"I don't forget that with Porto against Manchester United last season, in the 89th minute we were out and in the 90th we were in the quarter-finals," he added recalling his side's last-gasp away goal at Old Trafford.
"In the Premier League, only a great team can win and they must do it without luck," he added.
Mourinho, who took over at Chelsea in July, believes the relentless pace, physical pressure and quality of the Premier League set it apart from other competitions.
Aside from earning Chelsea their first title for 50 years, winning the Premier League would also tick an important box on Mourinho's list of personal ambitions.
"I have never won it. I like to win new things," he said.
OFF GUARD
Mourinho's self-belief and single-mindedness have caught his Premier League rivals off guard.
After Saturday's 4-0 romp over Norwich, the sixth time in nine league outings Chelsea have scored four, the south west London side moved six points clear of second-placed Everton, with perennial champions Arsenal and Manchester United also in their wake.
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Two of the goals, stylish though they were, had come from Norwich defensive slip-ups.
After the break Chelsea took heed of their perfectionist taskmaster and claimed complete control of the game, scoring once again and creating countless chances.
"I told them we needed to have a clear vision of the game, not to be influenced by the 3-0 scoreline but by our performance and our opponents' performance," Mourinho said. "We must forget individual things."
To a side bursting with expensive international talent and featuring the outstanding ball-skills of, among others, wingers Arjen Robben and Damien Duff, it takes a supremely assured boss to issue such instructions.
Mourinho has few rivals when it comes to confidence.
"In this moment I think nobody is better than us," he said.
"If we keep our condition, our physical and our mental condition, I think nobody can stop us."
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