Piriformis syndrome (PS) is an unusual cause of sciatica that, because of the lack of strict diagnostic criteria, remains a controversial clinical entity. The diagnosis of PS is still primarily clinical because no diagnostic tests have proven to be definitive. We report the case of a 30-year-old woman, affected by a severe scoliosis, who developed a persistent buttock pain resembling that of PS. The clinical suspicion was confirmed by magnetic resonance imaging (MRI) of the pelvis, which showed an enlargement of the left piriformis muscle with an anterior isplacement of the sciatic nerve. The role of MRI in the diagnosis, clinical definition, and therapeutic approach to PS is discussed.