The Ligue 1 champions saw Zlatan Ibrahimovic sent off in the first half for a lunge on Oscar but the Blues still didn't have enough to progress despite their numerical advantage.
Twice Chelsea took the lead, firstly through Gary Cahill on 81 minutes before David Luiz returned to haunt his former club with a thumping header that took the game into extra time.
Eden Hazard then tucked home a penalty after Thiago Silva was adjudged to have handled the ball in the area but the Brazil defender made amends with a dramatic equaliser on 114 minutes to see PSG through on away goals.
"Of course, we had the game in our hands twice but I think the opponent was stronger than us," Mourinho told Sky Sports. "They coped better than us with the pressure of the game. I think with them at 10 men we felt the pressure of winning even more.
"They had nothing to lose, they just played their game. We couldn't cope with that. We conceded two goals from set-pieces where the organisation is clear, where the markers have to decide and the players in the zone are the same. We conceded two goals that were difficult to accept."
Mourinho says Chelsea must now turn their focus to the Premier League and ensure they end the season by winning the title.
"I told my players as I always do that it's not after the match that I kick tables and doors," he added. "It's time to be calm and analyse the team because we have a game on Sunday and we have to win the Premier League.
"We are playing to win the Premier League and we have more matches to play."
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