The City forward, who grew up close to the national stadium, has worked with the club to give pupils from Ark Elvin Academy the opportunity to be at the game against Brighton.
Sterling, 24, was raised on the St Raphael's estate in Wembley and attended Copland Community School, which was renamed Ark Elvin in 2014.
Sterling met 10 pupils from the school on Thursday at City's Academy Campus, answering questions and presenting the tickets.
"I have a close connection to Ark Elvin Academy having attended the school myself when it was Copeland Community School, so it is great to be able to give these students the chance to watch a game at Wembley," he said. "I grew up right next door to the stadium and would dream of one day playing in a cup final or even representing my country there. "To now be able to play there myself is an honour and this is a great opportunity to give back to the community that helped me get to where I am."
Year 10 student Mamadou Diallo said: "Raheem is someone that's just like us and went to the same school. We know that if we work hard and follow our passion, we can do anything we want."
Sterling, who has a tattoo of himself as a young boy looking up at the stadium's iconic arch, has retained close links to the Wembley area and has looked into building a football academy nearby.
"I was from Wembley, I lived in Wembley," he said in 2016. "I lived on an estate [public housing] for a month until my mum got the place in Wembley.
"From eight to 14, I lived in Wembley. It's not the poshest area but for me it was an unbelievable area. It was lovely growing up there. I had a great green where there were trees and I used to eat apples there."
City have not sold their entire allocation for the FA Cup semifinal yet with around 25,000 of their 33,000 available tickets sold so far.
The semifinal will be the club's sixth visit to Wembley in 13 months and is followed by two return trips to London in the following seven days for the Champions League clash with Tottenham and Premier League game at Crystal Palace.
City returned 2,000 extra tickets back to the Football Association, which the club have said were the more expensive tickets, with prices going up to £120.
Sterling and City are on course for an unprecedented quadruple this season, with the Premier League, FA Cup Champions League still available to Pep Guardiola's side, who the Carabao Cup in February. And Kevin De Bruyne thinks Sterling will soon be adding trophies at international level too.
The Belgium international has said England have so much talent coming through that they should be considered the favourites for Euro 2020.
England have already reached the semifinals of this summer's League of Nations and with young players Jadon Sancho and Callum Hudson-Odoi making their debuts during their recent qualifiers, and De Bruyne is predicting the Three Lions will win a major tournament in the next decade.
"I told the England guys a week ago that you should win the Euros," the midfielder told reporters. "I think they are favourites, with France.
"I see the guys already established, and those coming up, so the future looks really good. Will they win it? I don't know, because only one team can win it but you have a chance to do well in the next 10 years."
City youngster Phil Foden has yet to be called up for the England senior squad yet but took another step closer with an impressive display in his first Premier League start on Wednesday in the 2-0 victory over Cardiff City.
"Give him time," De Bruyne added. "It's not because you play some games, and start a game, that you have to go into the national team.
"If he is in someone else will have to drop out -- top teams are like that.
"Gareth Southgate will do what he needs to do and if Phil progresses well he has a chance to go to the Euros next year. He will play enough games for England."