The Merseysiders slumped to a loss in front of a packed crowd at Boston's Fenway Park as goals from Michael Bradley and Alessandro Florenzi helped the Italians to a 2-1 win
Second half strikers from Michael Bradley and Alessandro Florenzi proved to be enough for the Giallorossi, despite a late effort from Reds' midfielder Charlie Adam.
Roma had the better of the early going and created the game's first real opening as Panagiotis Tachtsidis shot straight at Peter Gulacsi.
The Reds quickly grew into the contest and came close to taking the lead when Sterling was denied from close range by Romanian keeper Bogdan Lobont. Liverpool was soon back on the defensive however, as Gulacsi had to be called into action to turn an Osvaldo effort round the post after a fine break from the Italians.
Midfielder Jonjo Shelvey was at the center of the majority of Liverpool's attacks in the first half, and the 20-year-old almost netted a spectacular solo goal as he beat several Roma defenders before his shot was tipped away by Lobont, Eccleston followed up but his strike flew high and wide.
Liverpool continued in the ascendancy and fashioned the best chance of the opening period as Alberto Aquilani's through ball over the top found Joe Cole, the former Chelsea man showed great awareness to try and chip the ball over Lobont from long range but his effort bounced off the top of the crossbar.
Despite a high number of substitutions during the halftime interval the game continued to be played at a surprisingly fast tempo, and the deadlock was nearly broken three minutes after the break when substitute keeper Brad Jones produced a fine save with his feet to deny Tachtsidis from outside the box.
14 minutes later, the Serie A side did take the lead as American international Michael Bradley turned smartly inside the box before firing a low shot past Jones and into the bottom corner.
Roma's advantage was quickly doubled as a fine move was finished off by Alessandro Florenzi, who rolled the ball into an empty net after latching onto a flick from Erik Lamela.
The Serie A outfit appeared to be cruising to victory, but 10 minutes from time Liverpool gained a foothold in the contest as Adam fired in from the edge of the box after collecting a pass from Daniel Pacheco.
That goal proved to be little more than a consolation however as the Reds were unable to mount any kind of an incisive attack in the closing stages, condemning Rodgers' men to their first defeat as they continue their preparation for the new Premier League campaign.