Emotions have been shown to alter pain perception, but the underlying mechanism is unclear since emotions also affect attention, which itself changes nociceptive transmission. We manipulated independently direction of attention and emotional state, using tasks involving heat pain and pleasant and unpleasant odors. Shifts in attention between the thermal and olfactory modalities did not alter mood or anxiety. Yet, when subjects focused attention on the pain, they perceived it as clearly more intense and somewhat more unpleasant than when they attended to the odor. In contrast, odor valence altered mood, anxiety level, and pain unpleasantness, but did not change the perception of pain intensity. Pain unpleasantness ratings correlated with mood, but not with odor valence, suggesting that emotional changes underlie the selective modulation of pain affect. These results show that emotion and attention differentially alter pain perception and thus invoke at least partially separable neural modulatory circuits.