Investigating frontal EEG asymmetry as a possible biomarker of cognitive control abilities is especially important in ecological contexts such as school and work. We used a novel approach combining judgment performance and hemispheric frontal event-related potential (ERP) P300 asymmetry (fP3As) to evaluate aspects of cognitive control (i.e., repetition and switching) in adolescent females over a two-week ordinary school period. While undergoing electroencephalographic recording, students performed a word-colour “Stroop-like” congruence judgment task during morning and afternoon sessions, on Mondays and Wednesdays. Proportion of incongruence and congruence trials was 75% and 25%, respectively. ERP analysis revealed larger “novelty” right hemispheric fP3As amplitude for infrequent congruence but equivalent or significantly smaller than left hemispheric fP3As amplitude for frequent incongruence. RTs increased with extent of right fP3As shift. Behaviorally, repeat trial pairs (i.e., congruent followed by congruent, incongruent followed by incongruent) generally did not differ by time or day and were associated with near-ceiling accuracy. In contrast, switch trial pairs (i.e., congruent followed by incongruent, incongruent followed by congruent) in the afternoon were slower and associated with lower accuracy at the expected 75% criterion rate (i.e., judging incongruence by default), dropping significantly below 75% in the mornings. Crucially, compared to afternoon, morning fP3As patterns did not change adaptively with switch trial pairs. Although retroactive switching during congruence judgment was affected at all testing times, we conclude it was most impaired in the mornings of both early and mid school weeks, supporting misalignment between adolescent circadian cycle and school start time. We discuss some implications for optimal learning of adolescents at school.