Brain mechanisms linked to incorrect response selections made under time pressure during cognitive task performance are poorly understood, particularly in adolescents with attention‐deficit hyperactivity disorder (ADHD). Using subject‐specific multimodal imaging (electroencephalogram, magnetic resonance imaging, behavior) during flanker task performance by a sample of 94 human adolescents (mean age = 15.5 years, 50% female) with varying degrees of ADHD symptomatology, we examined the degree to which amplitude features of source‐resolved event‐related potentials (ERPs) from brain‐independent component processes within a critical (but often ignored) period in the action selection process, the stimulus‐response interval, were associated with motor response errors (across trials) and error rates (across individuals). Response errors were typically preceded by two smaller peaks in both trial‐level and trial‐averaged ERP projections from posterior medial frontal cortex (pMFC): a frontocentral P3 peaking about 390 ms after stimulus onset, and a premovement positivity (PMP) peaking about 110 ms before the motor response. Separating overlapping stimulus‐locked and response‐locked ERP contributions using a “regression ERP” approach showed that trial errors and participant error rates were primarily associated with smaller PMP, and not with frontocentral P3. Moreover, smaller PMP mediated the association between larger numbers of errors and ADHD symptoms, suggesting the possible value of using PMP as an intervention target to remediate performance deficits in ADHD.