With Lazio winning at Torino earlier in the evening to move within a point of its city rival, Roma could ill afford a slip but suffered a miserable evening as it ended the match with 10 men.
Lorenzo De Silvestri and Luis Muriel grabbed the goals for Sampdoria, which weathered a first-half storm before striking efficiently in the second half to boost its own hopes of qualifying for Europe next season.
Roma's sorry evening ended on an even worse note with Seydou Keita shown a red card late on as the Giallorossi also helped Juventus get one hand on a fourth straight Serie A title, thanks to its 14-point advantage with 11 games remaining.
Lazio won 2-0 at Torino courtesy of two goals in the space of seven minutes from Felipe Anderson late on.
The victory gives it a three-point cushion over Napoli in the hunt for the third Champions League berth, but it may have its sights set higher.
Fiorentina came from behind to pile the misery on Filippo Inzaghi and his AC Milan team with a 2-1 win at the Stadio Artemio Franchi.
Mattia Destro put the visitor in front against the run of play early in the second half, but Fiorentina fought back with goals from Gonzalo Rodriguez and Joaquin inside the final seven minutes earning it all three points.
As a result, Vincenzo Montella's side now trails fourth-placed Napoli by just one point with Lazio in third just four ahead.
Milan, meanwhile, remains in 10th place, 10 points behind the Viola with 11 games left to salvage its season.
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