Cortical auditory evoked potentials of instrumental musicians suggest that music expertise modifies pitch processing, yet less is known about vocal musicians. Mismatch negativity (MMN) to pitch deviances and difference limen for frequency (DLF) were examined among 61 young adult women, including 20 vocalists, 21 instrumentalists, and 20 nonmusicians. Stimuli were harmonic tone complexes from the mid-female vocal range (C4–G4). MMN was elicited by multideviant paradigm. DLF was obtained by an adaptive psychophysical paradigm. Musicians detected pitch changes earlier and DLFs were 50% smaller than nonmusicians. Both vocal and instrumental musicians possess superior sensory-memory representations for acoustic parameters. Vocal musicians with instrumental training appear to have an auditory neural advantage over instrumental or vocal only musicians. An incidental finding reveals P3a as a sensitive index of music expertise.