A crucial aspect of social decision-making is the ability to learn from the outcomes of preceding decisions. In particular, learning might be influenced by the expectedness of feedback and its valence. Expectedness has largely been operationalized as the frequency of stimulus occurrence and not in terms of its social context. Therefore, we investigated the influence of socially unexpected feedback, i.e., smiling upon adverse events, on behavioral and neural responses. We used a modified version of the ultimatum game, a commonly used paradigm for economic decision-making, by implementing different proposer identities with a distinct reaction pattern towards accepted and rejected monetary offers. We could show that an identity, who reacted with a smile towards rejected offers, evoked lower acceptance rates compared to identities, who reward acceptance with a smile. Electrophysiological correlates indicate N170 effects for emotional identities compared to a neutral control identity. Regarding FRN and P3 brain potentials, we detected a particular function of the smiling face when used as a socially unexpected, negative feedback stimulus. Hence, individuals seek an unexpected smile despite the associated monetary loss, which is accompanied by distinct neural patterns.