In western music, harmonic expectations can be fulfilled or broken by unexpected chords. Musical irregularities in the absence of auditory deviance elicit well-studied neural responses (e.g. ERAN, P3, N5). These responses are sensitive to schematic expectations (induced by syntactic rules of chord succession) and veridical expectations about predictability (induced by experimental regularities). However, the cognitive and sensory contributions to these responses and their plasticity as a result of musical training remains under debate. In the present study, we explored whether the neural processing of pure acoustic violations is affected by schematic and veridical expectations. Moreover, we investigated whether these two factors interact with long-term musical training. In Experiment 1, we registered the ERPs elicited by dissonant clusters placed either at the middle or the ending position of chord cadences. In Experiment 2, we presented to the listeners with a high proportion of cadences ending in a dissonant chord. In both experiments, we compared the ERPs of musicians and non-musicians. Dissonant clusters elicited distinctive neural responses (an early negativity, the P3 and the N5). While the EN was not affected by syntactic rules, the P3a and P3b were larger for dissonant closures than for middle dissonant chords. Interestingly, these components were larger in musicians than in non-musicians, while the N5 was the opposite. Finally, the predictability of dissonant closures in our experiment did not modulate any of the ERPs. Our study suggests that, at early time windows, dissonance is processed based on acoustic deviance independently of syntactic rules. However, at longer latencies, listeners may be able to engage integration mechanisms and further processes of attentional and structural analysis dependent on musical hierarchies, which are enhanced in musicians.