Surviving in a complex and changeable environment relies on the ability to extract probable recurring patterns. Here we report a neurophysiological mechanism for rapid probabilistic learning of a new system of music. Participants listened to different combinations of tones from a previously unheard system of pitches based on the Bohlen-Pierce scale, with chord progressions that form 3:1 ratios in frequency, notably different from 2:1 frequency ratios in existing musical systems. Event-related brain potentials elicited by improbable sounds in the new music system showed emergence over a 1 h period of physiological signatures known to index sound expectation in standard Western music. These indices of expectation learning were eliminated when sound patterns were played equiprobably, and covaried with individual behavioral differences in learning. These results demonstrate that humans use a generalized probability-based perceptual learning mechanism to process novel sound patterns in music.