We aimed to investigate the neurocognitive mechanisms of event congruency with prior (schema) knowledge for the learning of novel compound words. Event-related potentials (ERPs) were recorded during an incidental learning task, in which novel noun-noun compounds were presented in a semantically congruent context, enabling schema-supported processing, or in a neutral context. As expected, associative memory performance was better for compounds preceded by a congruent context. Although the N400 was attenuated in the congruent condition, subsequent memory effects (SMEs) in the N400 time interval did not differ across conditions, suggesting that the processes reflected in the N400 cannot account for the memory advantage in the congruent condition. However, a parietal SME was obtained for compounds preceded by a congruent context, only, which we interpret as reflecting the schema-supported formation of a conceptual compound representation. A late frontal SME was obtained in both conditions, presumably reflecting the more general inter-item associative encoding of compound constituents.