The occurrence of primacy versus recency effects in free recall is suggested to reflect either two distinct memory systems, or the operation of a single system that is modulated by allocation of attention and less vulnerable to interference. Behavioral and event-related brain potential (ERPs) measures were used to investigate the encoding substrates of the serial position curve and subsequent recall in young adults. Participants were instructed to remember lists of words consisting of 12 common nouns each presented once every 1.5 sec, with a recall signal following the last word to indicate that all remembered items should be written on paper. This procedure was repeated for 20 different word lists. Both performance and late ERP amplitudes reflected classic recall serial position effects. Greater recall and larger late positive component amplitudes were obtained for the primacy and recency items, with less recall and smaller amplitudes for the middle words. The late positive component was larger for recalled compared to unrecalled primacy items, but it did not differ between memory performance outcomes for the recency items. The close relationship between the enhanced amplitude and primacy retrieval supports the view that this positive component reflects one of a process series related to attentional gradient and encoding of events for storage in memory. Recency effects appear to index operations determined by the anticipation of the last stimulus presentation, which occurred for both recalled and unrecalled memory items. Theoretical implications are discussed.