Baldini will join the Serie A club in October or November of this year after the Euro 2012 qualifying campaign.
“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," said England manager Fabio Capello.
The FA are unsure as of yet if Baldini will return for the tournament itself next summer.
FA Chairman David Bernstein added: “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.”