A main distinction has been proposed between voluntary and automatic mechanisms underlying temporal orienting (TO) of selective attention. Voluntary TO implies the endogenous directing of attention induced by symbolic cues. Conversely, automatic TO is exogenously instantiated by the physical properties of stimuli. A well-known example of automatic TO is sequential effects (SEs), which refer to the adjustments in participants’ behavioral performance as a function of the trial-by-trial sequential distribution of the foreperiod between two stimuli. In this study a group of healthy adults underwent a cued reaction time task purposely designed to assess both voluntary and automatic TO. During the task, both post-cue and post-target event-related potentials (ERPs) were recorded by means of a high spatial resolution EEG system. In the results of the post-cue analysis, the P3a and P3b were identified as two distinct ERP markers showing distinguishable spatiotemporal features and reflecting automatic and voluntary a priori expectancy generation, respectively. The brain source reconstruction further revealed that distinct cortical circuits supported these two temporally dissociable components. Namely, the voluntary P3b was supported by a left sensorimotor network, while the automatic P3a was generated by a more distributed frontoparietal circuit. Additionally, post-cue contingent negative variation (CNV) and post-target P3 modulations were observed as common markers of voluntary and automatic expectancy implementation and response selection, although partially dissociable neural networks subserved these two mechanisms. Overall, these results provide new electrophysiological evidence suggesting that distinct neural substrates can be recruited depending on the voluntary or automatic cognitive nature of the cognitive mechanisms subserving TO.