Background: Caffeine intake in the form of chewing gum is characterized by rapid absorption and utilization. Objectives: The purpose of this study was to investigate the effects of caffeinated chewing gum on exercise performance and physiological responses in a systematic review. Methods: All articles were searched using the PubMed and Scopus databases to include articles published up to June 2024, following the Preferred Reporting Items for Systematic Evaluation and Meta-Analysis (PRISMA) protocol. Results: Thirty-two studies were finally included. Most studies have found that pre-exercise caffeinated chewing gum supplementation is effective in improving endurance, repetitive sprinting, lower limb strength, and sport-specific performance, as well as lowering rating of perceived exertion (RPE) or fatigue index even with lower dosages of caffeine. Sympathetic activation may be one of the mechanisms by which caffeinated chewing gum affects athletic performance. No significant effect on energy metabolism indicators (blood glucose, blood lactate, free fatty acids) was found. In addition, two studies found that caffeinated chewing gum reduced or maintained cortisol levels and increased testosterone levels. However, caffeinated chewing gum intake does not have an impact on catecholamines and β-endorphins. There have been inconsistent results for explosive performance, agility performance, and pain perception. Only a few studies have examined balance performance. In conclusion, a low dose of caffeine (100–300 mg or 2–4 mg/kg) in the form of chewing gum is rapidly absorbed and utilized, positively impacting most exercise and physiological performance. Conclusions: Future studies should also consider the performance variables of agility, pain perception, and explosive performance to gain a more comprehensive understanding of the effects of caffeinated chewing gum on sympathetic activation and exercise performance.