Event-related brain potentials (ERPs) were recorded during a serial reaction time (RT) task, where single deviant items seldom (Experiment 1) or frequently (Experiment 2) replaced 1 item of a repeatedly presented 10-item standard sequence. Acquisition of sequence knowledge was reflected in faster RTs for standard as compared with deviant items and in an enhanced negativity (N2 component) of the ERP for deviant items. Effects were larger for participants showing explicit knowledge in their verbal reports and in a recognition test. The lateralized readiness potential indicated that correct responses were activated with shorter latencies after training. For deviant items, participants with explicit knowledge showed an initial activation of the incorrect but expected response. These findings suggest that the acquisition of explicit and implicit knowledge is reflected in different electrophysiological correlates and that sequence learning may involve the anticipatory preparation of responses.