This study investigates potential differences in brain function among high-, average-, and low-performance college students using electroencephalography (EEG). We hypothesize that the increased academic engagement of high-performance students will lead to discernible EEG variations due to the brain’s structural plasticity. 61 third-year college students from identical majors were divided into high-performance (n = 20), average-performance (n = 21), and low-performance (n = 20) groups based on their academic achievements. We conducted three EEG experiments: resting state, Sternberg working memory task, and Raven progressive matrix task. Comprehensive analyses of the EEG data from the three experiments focused on power spectral density (PSD) and functional connectivity, with coherence (COH) employed as our primary metric for the latter. The results showed that in all experiments, there were no differences in working memory ability and IQ scores among the groups, and there were no significant differences in the power spectral densities of the delta, theta, alpha1, alpha2, beta, and gamma bands among the groups. Notably, on the Raven test, compared to their high-performing peers, low-performing students showed enhanced functional connectivity in the alpha 1 (8–9 Hz) band that connects the frontal and occipital lobes. We explored three potential explanations for this phenomenon: fatigue, anxiety, and greater cognitive effort required for problem-solving due to inefficient self-regulation and increased susceptibility to distraction. In essence, these insights not only deepen our understanding of the neural basis that anchors academic ability, but also hold promise in guiding interventions that address students’ diverse academic needs.