The Blues booked their place in the last four of the competition, where they will meet Real Madrid in the semi-finals, after seeing off the challenges of Atletico Madrid and FC Porto in the two previous rounds.
Chelsea have had a topsy-turvy season which has already seen one managerial alteration, with Thomas Tuchel replacing Frank Lampard in January.
Chelsea are still in with a chance of lifting silverware this season as they lock horns with Manchester City in the FA Cup semi-finals this weekend before turning their attentions to Los Blancos.
"The season started off a bit strange,” James told Chelsea’s official website.
"If you’d said we would have been here at the start of the season then we probably wouldn’t have believed you, but it just shows what’s possible with hard work, everyone getting their heads down and working as a team.
"When you come to the later stages of competitions, you know you’re going to come up against top-class teams. We need to be ready and at our best right from the start."
"You can’t go into games with any fear. You can acknowledge a good team but you can’t go in worrying.
"We’re a very good team as well. We have many strengths, we play to our strengths and I think that’s shown over recent weeks. I just hope we can continue our good form and keep improving as a team.
"As we’ve progressed in the tournament, obviously the games have got harder and it’s higher stakes.
"I’ve never been in this position before, like a lot of the other young lads, and we’re learning a lot on the way. It’s part of playing in Europe and in the Champions League. When you play against foreign teams, they know what to do to get through games so you sometimes have to give some back to them as well."
