The City forward, who was brought up in Brent within the shadow of the world famous stadium, struck the all-important winner on 56 minutes to hand the Three Lions the perfect start to their Group D campaign.
It capped a fine all-round display by the 26-year-old and was his first goal for his country in a major tournament.
Reflecting on the crucial win, Sterling said he was determined to make his mark in the showpiece occasion at England's national home.
“It’s a great feeling. I’ve always said if I played at Wembley in a major tournament, I have to score!,” Sterling said.
“Growing up two minutes down the road, I know I have to score here. It was a great feeling to finally do that.
“I couldn’t wait to get here and get started. I knew it would be a positive one.
“It was the first game and we needed a win. We stuck together.
“We headed the ball when we needed to, cleared it when we needed to and played some good football at times. I thought the boys were brilliant.
"We need to try to build on it and enjoy today. We have to focus. It's early days.
"We need to keep winning, have that winning mentality and keep going forward."
Sterling was also full of praise for team-mate Kalvin Philips who capped his own excellent performance with a sublime through-ball to set up the City man for the winner.
“Brilliant,” was Sterling’s verdict on the Leeds holding midfielder.
“He kept driving with the ball and it was a lovely bit of skill to come inside and a lovely, weighted pass.
“It’s great to get off with a win. Now we have that game to look forward to. Hopefully, we’ll go on to that and win again.”