The England forward, signed from Liverpool for £49million last week after an acrimonious transfer saga, found the net after just two minutes and 17 seconds against Roma at the vast Melbourne Cricket Ground.
The goal contributed to an entertaining contest in the Australian section of the International Champions Cup, which City went on to win 5-4 on penalties after a 2-2 draw at the end of 90 minutes.
Sterling's first touch in the game was inauspicious as he fell over the ball in the first minute but he more than made amends soon after.
The 20-year-old raced onto a clever chipped through-ball from the impressive Kelechi Iheanacho and coolly finished with a low shot.
Roma replied with a long-range strike from Miralem Pjanic but Iheanacho, a highly-rated 18-year-old Nigerian, then struck himself when he pounced on a wayward Ashley Cole backpass.
The Italians levelled again three minutes from time with a well-struck Adem Ljajic free-kick but City took the honours as the game went to a shootout.
Aleksandar Kolarov missed for City but goalkeeper Joe Hart came to the rescue, saving from Seydou Doumbia and Seydou Keita and impressively smashing one in himself.
Sterling was taken off at half-time - along with eight other City players - but manager Manuel Pellegrini was pleased with his display.
The Chilean told a post-match press conference: "Well it is always important for the strikers to score
He scored very early in the game.
"He just played 45 minutes
He has worked with our team for just a few days so I am very happy with the way he played.
"He demonstrated why he is here, he demonstrated not only his value as a player
He is a very young player so I think he will improve a lot in the future, playing with Yaya (Toure), David Silva and (Sergio) Kun Aguero.
"I am very happy for him and very happy for our team to have bought him."
Source : PA
Source: PA