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Studies show that a single bout of exercise confers cognitive benefits. However, many individuals use psychoactive substances such as caffeine to enhance cognitive performance. The effects of acute exercise in comparison to caffeine on cognition remain unknown. Furthermore, caffeine use is associated with withdrawal symptoms upon cessation. Whether acute exercise can reduce withdrawal symptoms also remains unknown. The objectives of this study were to compare the effects of acute moderate intensity aerobic exercise to caffeine on working memory (WM) and caffeine withdrawal symptoms (CWS). In Phase I, non-caffeine (n = 29) and caffeine consumers (n = 30) completed a WM assessment, followed by acute exercise and caffeine. In Phase II, caffeine consumers (n = 25) from Phase I underwent the WM assessment and reported CWS following a 12-hour deprivation period. Acute moderate intensity aerobic exercise and caffeine (1.2 mg/kg) significantly improved WM accuracy and reduced CWS comparably. WM performance was not reduced following caffeine deprivation.