Transcranial current stimulation is a neuromodulation technique used to modulate brain oscillations and, in turn, to enhance human cognitive function in a non-invasive manner. This study investigated whether cross-frequency coupled transcranial alternating current stimulation (CFC-tACS) improved working memory performance. Participants in both the tACS-treated and sham groups were instructed to perform a modified Sternberg task, where a combination of letters and digits was presented. Theta-phase/high-gamma-amplitude CFC-tACS was administered over electrode F3 and its four surrounding return electrodes (Fp1, Fz, F7, and C3) for 20 min. To identify neurophysiological correlates for the tACS-mediated enhancement of working memory performance, we analyzed EEG alpha and theta power, cross-frequency coupling, functional connectivity, and nodal efficiency during the retention period of the working memory task. We observed significantly reduced reaction times in the tACS-treated group, with suppressed treatment-mediated differences in frontal alpha power and unidirectional Fz-delta-phase to Oz-high-gamma-amplitude modulation during the second half of the retention period when network analyses revealed tACS-mediated fronto-occipital dissociative neurodynamics between alpha suppression and delta/theta enhancement. These findings indicate that tACS modulated top-down control and functional connectivity across the fronto-occipital regions, resulting in improved working memory performance. Our observations are indicative of the feasibility of enhancing cognitive performance by the CFC-formed tACS.