Manager Fabio Capello refused to confirm that he will hand the 25-year-old his debut, but during the squad's final training session Baines was part of what is expected to be the starting line-up.
Baines is battling it out with Aston Villa's Stephen Warnock for the left-back slot which has been left vacant by Ashley Cole's ankle injury and Wayne Bridge's retirement from international football.
When asked who would get the first chance to impress, Capello said: 'There are two choices at left-back, but only one at right-back - so Wes Brown will start.'
Both Baines and Warnock are expected to play some part in what is England's final friendly before Capello names his preliminary squad for the World Cup in South Africa.
Baines is just one of a number of Blues in action tonight with Jack Rodwell and Dan Gosling in the England Under-21s squad for their European Championship qualifier against Greece at Doncaster's Keepmoat Stadium.
Diniyar Bilyaletdinov is in Budapest for Russia's friendly with Hungary, while in Amsterdam goalkeeper Tim Howard and on-loan forward Landon Donovan will play for the USA against a Holland side which could include Blues defender John Heitinga.