Detecting one's agreement with or deviation from other people, a key principle of social cognition, relies on neurocognitive mechanisms involved in reward processing, mismatch detection, and attentional orienting. Previous studies have focused on explicit depictions of the (in)congruency of individual and group judgments. Here, we report data from a novel experimental paradigm in which participants first rated a set of images and were later simply confronted with other individuals’ ostensible preferences. Participants strongly aligned their judgments in the direction of other people's deviation from their own initial rating, which was neither an effect of regression toward the mean nor of evaluative conditioning (Experiment 1). Most importantly, we provide neurophysiological evidence of the involvement of fundamental cognitive functions related to social comparison (Experiment 2), even though our paradigm did not overly boost this process. Mismatches, as compared to matches, of preferences were associated with an amplitude increase of a broadly distributed N400‐like deflection, suggesting that social deviance is represented in the human brain in a similar way as conflicts or breaches of expectation. Also, both early (P2) and late (LPC) signatures of attentional selection were significantly modulated by the social (mis)match of preferences. Our data thus strengthen and valuably extend previous findings on the neurocognitive principles of social proof.