Chelsea won the competition for the first time last year but are now bidding to become the first team in the Champions League era to retain the title.
“It’s proven, so far, impossible for anyone to win it twice,” Di Matteo said.
“We’ll try to do the impossible.”
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The reputation of the Premier League means it is the most popular and one of the most watched leagues in the world.
Five English clubs will compete in the last sixteen of the Champions League for the first time ever as Liverpool, Manchester United, Manchester City, Chelsea and Tottenham face some difficult away matches.