He replaces injured Manchester City Wayne Bridge full-back in the Three Lions' squad for the friendly against Slovakia and World Cup qualifier with Ukraine, both at Wembley.
And the former Wigan Athletic defender, who made more than 150 appearances for the Latics, couldn't hide his delight at his first national selection, although he admits it is unlikely he will displace Chelsea defender Ashley Cole.
"I was delighted to be in the initial 30 and obviously even more so to be in the actual squad," he told the club's official website.
"It is a great honour to be selected for your country and, although I know it will be difficult to break into the actual team, I'm looking forward to the experience.
"What makes it even better is that two of my defensive team-mates at Everton are also in the squad and that reflects very well on how well we have been defending in the last few months."
Baines is the only uncapped member of Capello's squad, while there was a surprise inclusion for Tottenham centre-back Ledley King, who has been impressive in recent weeks despite struggling with injury to the extent that he rarely trains before matches.
Squad
Goalkeepers: David James, Ben Foster, Robert Green.
Defenders: Joleon Lescott, Phil Jagielka, Leighton Baines, Ashley Cole, Rio Ferdinand, Glen Johnson, Ledley King, John Terry, Matthew Upson.
Midfielders: Gareth Barry, David Beckham, Stewart Downing, Michael Carrick, Steven Gerrard, Frank Lampard, Aaron Lennon, Shaun Wright-Phillips.
Strikers: Wayne Rooney, Emile Heskey, Peter Crouch, Carlton Cole.
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