City beat PSG en route to their only previous semi-finals appearance in 2016 but the French have plenty of confidence having beaten title holders Bayern Munich in a quarter-final rematch of last year's final.
Record winners Real Madrid face Chelsea and last year's finalists Paris Saint-Germain are up against Manchester City as the UEFA Champions League (UCL) returns after a week of turmoil in the football community over an ill-fated Super League project.
Real, Chelsea and City are among 12 clubs listed while PSG declined to join the competition, reports DPA. An angry backlash from fans, federations and politicians prompted the six English clubs, Inter Milan and Atletico Madrid to announce their intention to withdraw.
The other four, which include Real have not made similar statements, and Real and Super League president Florentino Perez continues to defend the project, saying it is to save football.
UEFA president Aleksander Ceferin is among the biggest critics as the Super League was to compete directly with the Champions League which itself underwent a controversial reform last week.
Ceferin has not ruled out sanctions but for now the season continues as planned en route to the May 29 final in Istanbul.
Zinedine Zidane's Real have advanced over Atalanta and Liverpool into their first semi-final since 2018, and in La Liga as defending champions are fighting Barcelona and Atletico Madrid.
"We've not won anything yet, but we're alive in Europe and the Liga," Zidane said ahead of Tuesday's first-leg date.
Chelsea have shown big improvement since Thomas Tuchel became their manager in January, with the German aiming for his second straight final after 2020 with PSG.
The Blues ousted City last week in the FA Cup semi-finals and are unbeaten in three previous continental dates with Real, the last being the 1998 European Super Cup.
"There's a lot of confidence -- we have a great team, a very confident bunch of guys. We're going to go in and try to win this thing," said Chelsea's American forward Christian Pulisic.
While Real have an unrivalled 13 titles and Chelsea lifted the trophy in 2012, the ambitious duo of PSG and City finally wants to taste glory as well in the elite event, with one of them assured of making the final.
City beat PSG en route to their only previous semi-finals appearance in 2016 but the French have plenty of confidence having beaten title holders Bayern Munich in a quarter-final rematch of last year's final.
"We've eliminated the champions of Europe, we're in the semi-finals and we'll have to work even harder," PSG forward Neymar said.
City manager Pep Guardiola will be hoping for a good result on Wednesday in France as he aims to end his Champions League jinx after leaving Barcelona where he won the trophy twice.
City, who won a fourth straight English League Cup on Sunday against Tottenham Hotspur, can theoretically clinch the Premier League next weekend but a first European Cup would be the icing on the cake.
"We won the first one, we are close to a second one and we go to Paris to try for another one," Guardiola said. "We will rest and prepare for the semi-final first leg against PSG. After that, we are two games away from winning the most important title."
