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The biased competition model proposes that there is top-down directing of attention to a stimulus matching the contents of working memory (WM), even when the maintenance of a WM representation is detrimental to target relevant performance. Despite many studies elucidating that spatial WM guidance can be present early in the visual processing system, whether visual WM guidance also influences perceptual selection remains poorly understood. Here, we investigated the electrophysiological correlates of early guidance of attention by WM in humans. Participants were required to perform a visual search task while concurrently maintaining object representations in their visual WM. Behavioral results showed that response times (RTs) were longer when the distractor in the visual search task was held in WM. The earliest WM guidance effect was observed in the P1 component (90–130 ms), with match trials eliciting larger P1 amplitude than mismatch trials. A similar result was also found in the N1 component (160–200 ms). These P1 and N1 effects could not be attributed to bottom-up perceptual priming from the presentation of a memory cue, because there was no significant difference in early event-related potential (ERP) component when the cue was merely perceptually identified but not actively held in WM. Standardized Low Resolution Electrical Tomography Analysis (sLORETA) showed that the early WM guidance occurred in the occipital lobe and the N1-related activation occurred in the parietal gyrus. Time-frequency data suggested that alpha-band event-related spectral perturbation (ERSP) magnitudes increased under the match condition compared with the mismatch condition only when the cue was held in WM. In conclusion, the present study suggests that the reappearance of a stimulus held in WM enhanced activity in the occipital area. Subsequently, this initial capture of attention by WM could be inhibited by competing visual inputs through attention re-orientation, reflecting by the alpha-band rhythm.