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It put City 3-1 up on aggregate and took Sterling to a century of goals for the club.
The 25-year-old is the 17th player to achieve the feat for City, though he is the first Englishman to reach triple figures sinceDennis Tueart in 1981.
It took Sterling 242 matches to reach the milestone, while the England star has also notched 74 assists during those games.
Sterling, who went close to a second moments after his opener before Karim Benzema equalised, is also the sixth English player to score at least 20 Champions League goals – following Wayne Rooney, Paul Scholes, Frank Lampard, Steven Gerrard and Harry Kane.
Only Rooney – aged 24 years and157 days –reached the total at a younger age than the City forward.
Sterling has been in strong goalscoring form again in 2019-20, and recently surpassed Cristiano Ronaldo on the Premier League's all-time scoring list when he notched his 85th career goal.
Overall, Sterling scored 20 times in the Premier League in 2019-20, setting a new career high in the competition after scoring 17 the previous year and 18 the season before that.
His exploits, however, weren't enough to earn Man City a third straight Premier League title, as Guardiola's men finished in second place, 18 points behind runaway champions Liverpool.
Sterling continued to be a champion for important causes off the pitch as well, which greatly impressed his manager.
"I think Raheem and many, many of our players, a lot of people are trying to make a better world," Guardiola said.