The home side were boosted by the return after injury of talismanic skipper Francesco Totti, while Wayne Bridge started at left-back for the Blues.
It took ten minutes for the first shot on goal to materialise, as Deco moved into space and tried his luck from all of 30 yards, forcing Alexander Doni into a smart, diving save away to his right.
Four minutes later, Mirko Vucinic did well to beat a series of challenges and, after getting the ball back, lofted an effort from 25 yards narrowly over the top of Petr Cech's crossbar.
Twenty-two minutes in Frank Lampard tested Doni with a long-range effort and on the half-hour mark the Roma keeper had to push away another strike from distance from the England midfielder.
Eleven minutes before half-time it was the home side who broke the deadlock, as Chelsea were caught cold from a set-piece.
David Pizarro played a free-kick out to Cicinho on the right flank and his cross was turned home from close range at the near post by the unmarked Christian Panucci.
That goal enthused the home side, who held on to their lead up to the interval, when Chelsea made a double substitution.
However, three minutes into the second period it was 2-0 to Roma as Matteo Brighi fed Vucinic and he rifled a 20-yard right-foot shot into the corner of the net past the helpless Cech.
Just before the hour mark it was game over as the home side stretched their lead to three goals, after Vucinic had dispossessed John Obi Mikel near the halfway line.
The striker then advanced on goal before coolly despatching a low right-foot shot past Cech at his near post.
Fifteen minutes from time, Chelsea registered a consolation as Deco fired the ball into the area and after Doni blocked his initial effort, John Terry turned the ball in from close range.
However, the Blues' miserable evening was topped off five minutes later as Deco was shown a second yellow card and then a red for trying to take a free-kick too quickly.