The event-related potential (ERP) N450 component has been described in rhyme detection tasks as a negative response elicited by non-rhyming words in comparison to rhyming ones. This response, which peaked around 450 ms over the midline and right hemisphere recording sites, has been subsequently suggested to start already at approximately 300 ms. Moreover, although, the phonological N450 has first been linked to the semantic N400 component, its cognitive nature and cerebral origin remained debated. In this study, we re-investigated the time course of the electrophysiological responses to rhyming and non-rhyming words and estimated their cerebral generators using source localization methods. Waveform analysis showed that, prior to the N450 response to non-rhyming, a slightly earlier negativity characterized the rhyming condition over left fronto-temporal electrodes and peaked at approximately 350 ms. The analysis of the ERP map series in terms of functional microstates revealed a specific map segment in the rhyming condition and another one in the non-rhyming condition. Source localization indicated that the rhyming-elicited microstate engaged predominantly left frontal and temporal areas while the non rhyming-specific response recruited temporal and parietal regions bilaterally. Our results suggest that, similar to the N400 component that is also induced by mismatch contexts, the N450 might rely on temporal generators.