Although it is now well documented that observation by others can be a powerful elicitor of prosocial behaviour, the underlying neural mechanism is yet to be explored. In the present fMRI study, we replicated the previously reported observer effect in ethical consumption, in that participants were more likely to purchase social products that are sold to support people in need than non-social products when being observed by others. fMRI data revealed that the anterior cingulate cortex (ACC) and the dorsomedial prefrontal cortex (dmPFC) encoded subject-specific value parameters of purchase decisions for social and non-social products, respectively, under social observation. The ACC showed strong functional coupling with the amygdala and the anterior insula when participants in the observation condition were making purchases of social versus non-social products. Finally, ventromedial prefrontal cortex (vmPFC) activity predicted faster reaction time and increased prosocial behavior during decisions to purchase social versus non-social products, regardless of social observation. The present findings suggest that subregions of the mPFC, namely the dmPFC, ACC, and vmPFC, are hierarchically organized to encode different levels of decision values from the value of context-sensitive reputation to that of internalized prosociality.