The Manchester United boss believes England are "really strong" and have enough skill to spring a major surprise and lift the trophy in Russia this summer.
It is a major vote in confidence from The Special One for Gareth Southgate's World Cup campaign as England look to end the nation's 52-year drought since their 1966 victory.
With England preparing for their Group G opener against Tunisia on Monday, Mourinho believes the squad will have no issues thanks to their Champions League expertise.
"They have a good group of young but experienced players.
"All of them play in the most competitive competition in the world, the Premier League, all of them playing for the best teams with experience of playing in the Champions League, which is a high level of football, obviously."
Four Manchester United players including Jesse Lingard Marcus Rashford, are included and their coach is confident England can impress Russia.
"Yes, I think they can do it," he added.
The Portuguese manager also believes World Cup favourites Brazil and Germany have the most balanced squad but did not expect the hosts to win big.
"They have good squads but good squads don't always make good teams... (but) I don't think the underdogs will make a big surprise," he said. "In the end, the top teams in South America and Europe are the ones that will be fighting for the title."
England have been off to a good start induring the build-up with wins over Nigeria and Costa Rica and Southgate wants to maintain that buzz for the opener.
Speaking earlier this week, Southgate said he was proud of his team and is excited for the campaign to officially start.
He said: "I think we're all looking forward to getting on with the tournament now, there's been such a long preparation. We've had weeks now together and with a really good training camp and really pleased with the performances in the two games."
The squad landed in St Petersburg and is based in the nearby village of Repino, in north-west Russia.
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