Recent work in interpersonal coordination has revealed that neural oscillations, occurring spontaneously in the human brain, are modulated during the sensory, motor, and cognitive processes involved in interpersonal interactions. In particular, alpha-band (8–12 Hz) activity, linked to attention in general, is related to coordination dynamics and empathy traits. Researchers have also identified an association between each individual’s attentiveness to their co-actor and the relative similarity in the co-actors’ roles, influencing their behavioral synchronization patterns. We employed music ensemble performance to evaluate patterns of behavioral and neural activity when roles between co-performers are systematically varied with complete counterbalancing. Specifically, we designed a piano duet task, with three types of co-actor dissimilarity, or asymmetry: (1) musical role (starting vs. joining), (2) musical task similarity (similar vs. dissimilar melodic parts), and (3) performer animacy (human-to-human vs. human-to-non-adaptive computer). We examined how the experience of these asymmetries in four initial musical phrases, alternatingly played by the co-performers, influenced the pianists’ performance of a subsequent unison phrase. Electroencephalography was recorded simultaneously from both performers while playing keyboards. We evaluated note-onset timing and alpha modulation around the unison phrase. We also investigated whether each individual’s self-reported empathy was related to behavioral and neural activity. Our findings revealed closer behavioral synchronization when pianists played with a human vs. computer partner, likely because the computer was non-adaptive. When performers played with a human partner, or a joining performer played with a computer partner, having a similar vs. dissimilar musical part did not have a significant effect on their alpha modulation immediately prior to unison. However, when starting performers played with a computer partner with a dissimilar vs. similar part there was significantly greater alpha synchronization. In other words, starting players attended less to the computer partner playing a similar accompaniment, operating in a solo-like mode. Moreover, this alpha difference based on melodic similarity was related to a difference in note-onset adaptivity, which was in turn correlated with performer trait empathy. Collectively our results extend previous findings by showing that musical ensemble performance gives rise to a socialized context whose lasting effects encompass attentiveness, perceptual-motor coordination, and empathy.