Fioricet Fioricet Fioricet is a barbiturate sedative mixed with a non-aspirin pain medication and caffeine. This non-narcotic pain medication and relaxant is often prescribed for tension headaches caused by contractions of the muscles in the neck and shoulder area, and migraine.Fioricet Fioricet Fioricet is a barbiturate sedative mixed with a non-aspirin pain medication and caffeine. This non-narcotic pain medication and relaxant is often prescribed for tension headaches caused by contractions of the muscles in the neck and shoulder area, and migraine.