The Italian will leave his post with the Three Lions to join the Serie A club, but it has not yet been decided whether he will stay on for the tournament if Capello's side qualify
Baldini will continue working under Fabio Capello until the Autumn, and will not commence his work with the Italian side until England have completed their qualification campaign.
It is still to be decided whether he will return to his post for a friendly scheduled to take place in February or for the European Championships in 2012 if England qualify.
Capello told the FA's official website: “Franco has been given a good opportunity by Roma, but I am happy he will stay with me and the England team until after the qualification programme. For me this is very important. We can decide after this if Franco will be with us for the European Championships.”
FA chairman David Bernstein said: “We respect his decision to accept the offer from Roma. I would like to thank Franco for the professional way in which he has handled this and maintained his sole commitment to working with Fabio and the team until after the qualifying games.”