The English international scored the only goal of the game from the penalty spot, calmly stroking the ball straight down the middle beyond the diving Jose Sa in the second half.
He becomes just the 32nd player to score 100 goals in the competition, 82 of which have been scored for City, with the other 18 coming during his time at Liverpool.
He is the eighth youngest player to reach a Premier League century at 27 years and three days.
And afterwards, Sterling revealed his pride at reaching the milestone.
“It’s a lovely achievement,” he said. “Some fantastic players in there, I really wanted to be in among them.
“We had to keep patient, they kept it tight and we knew if we kept playing we’d eventually break through.
“We keep saying the next game, the next game, we’ve done that again today and now we look forward to midweek.”
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The visitors were rigid in defence early on but went down to ten men after striker Raul Jimenez was given two yellow cards in the space of 31 seconds just before the interval.
Led by skipper Conor Coady, Wolves remained resolute, with some last-ditch blocks denying City more goals after the opener.
Sterling believes that Wolves always provide a stern test for Pep Guardiola‘s side.
“Every time we play Wolves at home it’s always a difficult one,” he admitted.
“It’s always a tough one, they’re always a difficult side to play against. Each game has its own challenges.
“We’ve always found it difficult to break Wolves down. It was the same today.”
