Baines has been watched closely by coach Fabio Capello recently and the Everton's defender's impressive performances mean he has got the chance to act as understudy to first-choice left-back now Wayne Bridge has been sidelined by a hamstring injury.
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And despite not being able to train, King has been handed his first call-up during the Capello regime as the England coach takes a closer look at the Tottenham man.
As expected, Manchester United goalkeeper Ben Foster makes the cut - also for the first time since Capello took charge.
Earlier this week, the Italian spoke in glowing terms about Foster and said he was willing to make an exception to his unwritten rule to leave out players who do not play regularly for their clubs.
Also involved is Aaron Lennon, who won the last of his nine caps against Andorra two years ago but has been doing well for Tottenham lately and was instrumental in their win over Chelsea yesterday.
But there was bad news for Aston Villa pair Ashley Young and Gabriel Agbonlahor, neither of whom keep their places from last month's friendly defeat to Spain in Seville.
As Carlton Cole is among those who remain, Capello presumably feels the draining confidence at Villa Park is having an adverse effect on the pair.
With Wayne Rooney and Steven Gerrard back for the first time since the qualifying win in Belarus last October and Rio Ferdinand fit after missing the Seville reverse with a stomach bug, England should be at full strength next weekend.
Capello has already pledged to make maximum use of his six allotted substitutes against Slovakia, with the crunch clash against Ukraine uppermost in his thoughts.
England squad for matches against Slovakia and Ukraine:Foster (Man Utd), Green (West Ham), James (Portsmouth); Baines (Everton), ACole (Chelsea) Ferdinand (Man Utd), Jagielka (Everton), Johnson (Portsmouth),King (Tottenham), Lescott (Everton), Terry (Chelsea), Upson (West Ham); Barry(Aston Villa), Beckham (LA Galaxy), Carrick (Man Utd), Downing (Middlesbrough),Gerrard (Liverpool), Lampard (Chelsea), Lennon (Tottenham), Wright-Phillips (ManCity); C Cole (West Ham), Crouch (Portsmouth), Heskey (Aston Villa), Rooney (ManUtd).