The present study investigates the neural pathways underlying individual susceptibility to affective or cognitive information in persuasive communication, also known as the structural matching effect. Expanding on the presumed involvement of the ventromedial prefrontal cortex (vMPFC) in persuasion, we hypothesized that the vMPFC contributes to the evaluation of persuasive information depending on its match with the recipient’s affective or cognitive predominance. During functional magnetic resonance imaging, 30 participants evaluated 10 consumable products presented with both affective and cognitive persuasive messages. All participants were characterized on a continuum regarding their personal orientation in terms of individual differences in need for affect (NFA) and need for cognition (NFC). The results showed that the vMPFC, posterior cingulate cortex, and cerebellum are more strongly activated when the persuasive message content, either affective or cognitive, matched the recipient’s individual affective or cognitive orientation. Interestingly, this effect in the vMPFC was found specifically when participants evaluated the products presented by the persuasive messages, whereas the correlation in the posterior cingulate cortex and cerebellum activity was detected when reading the messages. These results confirm the hypothesis that the vMPFC plays a role in subjectively weighting persuasive message content depending on individual differences in affective and cognitive orientation. Such a structural matching effect might involve the vMPFC particularly during explicit expressions of subjective valuations. These novel findings also further develop the conceptualisation of the role of the vMPFC in self-related processing.