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Background: In the oddball paradigm, the dorsolateral prefrontal cortex (DLPFC) is often associated with active cognitive responses, such as maintaining information in working memory or adapting response strategies. While some evidence points to the DLPFC’s role in passive auditory deviance perception, a detailed understanding of the spatiotemporal neurodynamics involved remains unclear. Methods: In this study, event-related optical signals (EROS) and event-related potentials (ERPs) were simultaneously recorded for the first time over the prefrontal cortex using a 64-channel electroencephalography (EEG) system, during passive auditory deviance perception in 12 right-handed young adults (7 women and 5 men). In this oddball paradigm, deviant stimuli (a 1500 Hz pure tone) elicited a negative shift in the N1 ERP component, related to mismatch negativity (MMN), and a significant positive deflection associated with the P300, compared to standard stimuli (a 1000 Hz tone). Results: We hypothesize that the DLPFC not only participates in active tasks but also plays a critical role in processing deviant stimuli in passive conditions, shifting from pre-attentive to attentive processing. We detected enhanced neural activity in the left middle frontal gyrus (MFG), at the same timing of the MMN component, followed by later activation at the timing of the P3a ERP component in the right MFG. Conclusions: Understanding these dynamics will provide deeper insights into the DLPFC’s role in evaluating the novelty or unexpectedness of the deviant stimulus, updating its cognitive value, and adjusting future predictions accordingly. However, the small number of subjects could limit the generalizability of the observations, in particular with respect to the effect of handedness, and additional studies with larger and more diverse samples are necessary to validate our conclusions.