Sterling, 17, was previously representing the Under-19s but won a shock call-up to the senior squad for the World Cup qualifier against Ukraine last month, before being an unused substitute for the 1-1 draw at Wembley.
Now Sterling's encouraging form in the early part of the season for Liverpool has been rewarded again by his inclusion in Pearce's squad for the crucial two-legged fixture - with England hosting Serbia on October 12 and travelling to Krusevac four days later.
“For Raheem, to have an insight into the senior team, is fantastic,” said Pearce.
“He’s been in our development squads and has done extremely well for Liverpool, and credit to Brendan [Rodgers] who has given him his chance. We are pleased to have him."
Manchester United midfielder Nick Powell - a summer signing from Crewe Alexandra - has also won his first Under-21 call-up and joins Tottenham's Andros Townsend in the squad.
Team GB keeper Jack Butland - England's third choice during Euro 2012 - is also in the squad, along with Liverpool midfielder Jordan Henderson and Manchester City's new signing Jack Rodwell, both of whom have senior caps.
“We have to put as strong a squad as possible out,” Pearce said. “If you don’t do that at this stage of the competition, then you can make life very difficult for yourself.
“In the side for our play-off against Romania two years ago we had nine players who have all gone on to play for the senior team.
“Andros Townsend has also done well and has been around Tottenham’s first team squad consistently this year. Nick Powell got his move from Crewe, to a massive club at United, and has made his first team bow. He has a really bright future. I’m really looking forward to bringing them into the squad to give us a lift. They couldn’t come in at a more crucial time.
“Roy [Hodgson] and I have had a really good conversation in relation to my squad, last night being the last time we spoke, and he is more than aware of the Under-21s' key players. What’s certain is the players are at the centre of the decisions both Roy and I make.”
England are aiming to make the finals of the European Championships, held next summer, for the fourth successive time.
Goalkeepers: Ben Amos (Hull City - loan from Manchester United), Jack Butland (Birmingham City), Declan Rudd (Norwich City), Jason Steele (Middlesbrough)
Defenders: Ryan Bennett (Norwich City), Steven Caulker (Tottenham Hotspur), Nathaniel Clyne (Southampton), Craig Dawson (West Bromwich Albion), Tom Lees (Leeds United), Jack Rodwell (Manchester City), Danny Rose (Sunderland - loan from Tottenham Hotspur), Adam Smith (Tottenham Hotspur), Andre Wisdom (Liverpool)
Midfielders: Jordan Henderson (Liverpool), Tom Ince (Blackpool), Henri Lansbury (Nottingham Forest), Jason Lowe (Blackburn Rovers), Josh McEachran (Middlesbrough - loan from Chelsea), Nick Powell (Manchester United), Jonjo Shelvey (Liverpool), Raheem Sterling (Liverpool), Wilfried Zaha (Crystal Palace)
Forwards: Nathan Delfouneso (Blackpool - loan from Aston Villa), Marvin Sordell (Bolton Wanderers), Andros Townsend (Tottenham Hotspur), Connor Wickham (Sunderland).