Liverpool winger Sterling, 17, was a shock late addition to the senior party for last month's World Cup qualifying Group H draw with Ukraine and was being tipped to be selected again for the October 12 clash with San Marino and trip to Poland four days later.
Instead, he has been added to the under-21 squad for their two-legged European Championship play-off against Serbia on the same dates.
Young Lions boss Stuart Pearce considered calling up Sterling for last month's final Group Eight qualifiers against Azerbaijan and Norway but was convinced to leave him with the under-19s by Liverpool boss Brendan Rodgers.
Sterling, who has made eight appearances for the Reds this season, was joined in a 26-man under-21 squad by fellow newcomers Nick Powell and Andros Townsend ahead of the first leg of their play-off at Norwich's Carrow Road.
Manchester United youngster Powell hit the headlines last month when he scored on his Premier League debut against Wigan following his summer move from Crewe, while fellow midfielder Townsend was rewarded for his performances for Tottenham this season.
Pearce said: "For Raheem, to have an insight into the senior team, is fantastic.
"He's been in our development squads and has done extremely well for Liverpool, and credit to Brendan, who has given him his chance. We are pleased to have him.
"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 long conversation, last night being the last time, 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.''
Squad in full: Ben Amos (Hull City - loan from Manchester United), Jack Butland (Birmingham City), Declan Rudd (Norwich City), Jason Steele (Middlesbrough), 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), 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), Nathan Delfouneso (Blackpool - loan from Aston Villa), Marvin Sordell (Bolton Wanderers), Andros Townsend (Tottenham Hotspur), Connor Wickham (Sunderland).
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