"Last season they went out at this stage and I think this season they will be out," said Mourinho.
"They can win the game and the game in Dortmund but it's not enough, so I think they are out early for a second successive time and that must be difficult for them. They can win, but eight points is not enough so City will be the big team that will be out.
"They are a team that could win the competition. It's normal if a big team does not win it because there are other teams with the same power and desire and responsibilities and only one can win.
"It's not normal when you are out at the early stage. I speak for myself. If Real Madrid loses the final, the semi or even quarter-final, that's football. But when you are out at the group stage it's hard to accept and understand.
"It's a difficult group and we've known a big team or two would be out so every mistake is costly. Every game is a risk.
"Other teams have easy groups and know from day one they will qualify easy. City, Real Madrid and Borussia want to win but we all knew we could be out in the group, especially because Ajax are taking points.
"That first game (in Madrid) was crucial. If City had won that, the history would be a different history, but we won that match and now we are in a position where we depend only on ourselves and we are in a good condition to qualify. So I repeat I think City will be out."
Mourinho does not appear to feel the same love in Spain as he did in the Premier League, and he cannily charms the English media whenever the opportunity arises.
He was in charismatic form again, not disguising how much he relishes returning to this country.
"Yes, I never hide my feelings even if that makes some people not so happy. But I always said how much I loved my time here and I always like to be back," he said.
"I know in England you have difficult matches and opponents and atmospheres because crowds are strongly behind the team. I like and enjoy that and I know my players are happy to play in England."
Asked to compare the relative strengths of the competing leagues, he said: "In this moment the Spanish league has three teams in the top separated from the others by many points. And during the season that gap will be bigger.
In the Premier League you have now four teams and probably Tottenham and Arsenal should be there. More teams are equal and maybe it's more competitive because of that.
"The football and atmosphere is different. The respect is different. The press is different. The beauty of my experience is I had the chance to leave my country to be in England, Italy and Spain and get the best and worst of these experiences to make me a better manager.
"When you have those experiences, you evaluate, decide where you are happier and make the choice for the future."
He will be celebrating his 100th Champions League fixture tonight.
He said he would reflect on positive and negative experiences in the competition he has won twice as a coach.
"The two favourite memories are the two finals because we set out to win and won. The two negatives would be the two semi-final defeats on penalties.
"There is a third, which I won't talk about."
Asked about memorable ties, he said: "There are many, but I mainly remember the Manchester United-Porto game (at Old Trafford) that made us feel that we could be European champions.
"Also the Chelsea-Barcelona match where we won 4-2.
"The Inter-Barcelona semi-final, when Milan won 3-1 and in the second leg, the one I call the game of heroes at Camp Nou, when we were reduced to 10 for more than an hour is special because we were able to lead Inter to the final in Madrid."