Decisions about whether we like someone are often made so rapidly from first impressions that it is difficult to examine the engagement of neural structures at specific points in time. Here, we used a temporally extended decision-making paradigm to examine brain activation with functional MRI (fMRI) at sequential stages of the decision-making process. Activity in reward-related brain structures-the nucleus accumbens (NAC) and orbitofrontal cortex (OFC)-was found to occur at temporally dissociable phases while subjects decided which of two unfamiliar faces they preferred. Increases in activation in the OFC occurred late in the trial, consistent with a role for this area in computing the decision of which face to choose. Signal increases in the NAC occurred early in the trial, consistent with a role for this area in initial preference formation. Moreover, early signal increases in the NAC also occurred while subjects performed a control task (judging face roundness) when these data were analyzed on the basis of which of those faces were subsequently chosen as preferred in a later task. The findings support a model in which rapid, automatic engagement of the NAC conveys a preference signal to the OFC, which in turn is used to guide choice.