There is an extensive body of research showing a significant relationship between frontal midline theta activity in the 4- to 8-Hz range and working memory (WM) performance. Transcranial alternating current stimulation (tACS) is recognized for inducing lasting changes in brain oscillatory activity. Across two experiments, we tested whether WM could be improved through tACS of dorsomedial PFC and ACC, by affecting executive control networks associated with frontal midline theta. In Experiment 1, after either a 20-min verum or sham stimulation applied to Fpz–CPz at 1 mA and 6 Hz, 31 participants performed WM tasks, while EEG was recorded. The tasks required participants to either mentally manipulate memory items or retain them in memory as they were originally presented. No significant effects were observed in behavioral performance, and we found no change in theta activity during rest and task after stimulation. However, alpha activity during retention or manipulation of information in WM was less strongly enhanced during the delay period after verum stimulation as compared with sham. In Experiment 2 ( n = 25), tACS was administered during the task in two separate sessions. Here, we changed the order of the stimulation blocks: A 25-min task block was either accompanied first by sham stimulation and then by verum stimulation, or vice versa. Again, we found no improvements in WM through either tACS after-effects or online stimulation. Taken together, our results demonstrate that theta frequency tACS applied at the midline is not an effective method for enhancing WM.