Sterling is only 17 but has been rewarded for an encouraging start to life under Brendan Rodgers with a shock call-up to the senior England side.
If he plays, he will be the fourth-youngest player to win a full England cap behind Theo Walcott, Wayne Rooney and James Prinsep - who faced Scotland in 1879.
The winger had been with England's Under-19 team but will now form part of the squad that takes on Ukraine at Wembley on Tuesday evening, despite having made only seven first-team appearances in his career.
Spurs midfielder Livermore and Southampton's Lallana have also been asked to help make up the numbers in a squad badly affected by injury problems, though none of the three new call-ups will not have time to train before taking their places on the bench.
Lallana has admitted he thought Southampton manager Nigel Adkins was having a laugh when he told him he had been called up by England.
"I didn't think the gaffer was being serious when he called to tell me this morning," Lallana told Southampton's official website. "I was at home about to head into the training ground when he called - I must have asked if he was having me on a dozen times! I'm totally shocked to be honest."
Hodgson was forced to bring in new faces after Walcott and Daniel Sturridge were both absent from England's training session on Monday morning due to illness.
The duo trained on Sunday but did not participate in the session at Arsenal's London Colney training complex. The Football Association said the pair were "unwell" and Walcott was later told to return to Arsenal.
Walcott replaced Alex Oxlade-Chamberlain after 58 minutes of England's comfortable win in Chisinau while Sturridge was an unused substitute.
Ashley Young, Wayne Rooney, Andy Carroll and Adam Johnson had already been ruled out due to injury.
In defence, Chelsea captain John Terry has joined team-mate Ashley Cole in withdrawing from the squad after sustaining an injury against Moldova.
Meanwhile, a weekend surge in ticket sales means 68,000 have been sold for the clash against the Ukrainians, the Football Association confirmed.
The figure includes 6,500 which have been sold to Olympic Games volunteers at the reduced price of £20.12.
At half-time, 15 Team GB medallists will be presented to the crowd.