The primary aim of the current study was to employ event-related potentials (ERPs) methodology to disentangle the mechanisms related to inhibitory control in older adults with Williams syndrome (WS). Eleven older adults with WS (mean age 42), 16 typically developing adults (mean age 42) and 13 typically developing children (mean age 12) participated in the study. ERPs were recorded during a three-stimulus visual oddball task, during which participants were required to make a response to a rare target stimulus embedded in a train of frequent non-target stimuli. A task-irrelevant infrequent stimulus was also present at randomised intervals during the session. The P3a latency data response related to task-irrelevant stimulus processing was delayed in WS. In addition, the early perceptual N2 amplitude was attenuated. These data are indicative of compromised early monitoring of perceptual input, accompanied by appropriate orientation of responses to task-irrelevant stimuli. However, the P3a delay suggests inefficient evaluation of the task-irrelevant stimuli. These data are discussed in terms of deficits in the disengagement of attentional processes, and the regulation of monitoring processes required for successful inhibition.