Musicians exhibit enhanced perception of emotion in speech, although the biological foundations for this advantage remain unconfirmed. In order to gain a better understanding for the influences of musical experience on neural processing of emotionally salient sounds, we recorded brainstem potentials to affective human vocal sounds. Musicians showed enhanced time-domain response magnitude to the most spectrally complex portion of the stimulus and decreased magnitude to the more periodic, less complex portion. Enhanced phase-locking to stimulus periodicity was likewise seen in musicians’ responses to the complex portion. These results suggest that auditory expertise engenders both enhancement and efficiency of subcortical neural responses that are intricately connected with acoustic features important for the communication of emotional states. Our findings provide the first biological evidence for behavioral observations indicating that musical training enhances the perception of vocally expressed emotion in addition to establishing a subcortical role in the auditory processing of emotional cues.