Caffeine is widely used in sport and exercise because of its established ergogenic effects, yet problematic use, dependence, and withdrawal in athletic populations remain poorly characterized. This structured narrative review used a systematic database search and prespecified selection process to identify studies directly addressing problematic caffeine use, dependence, use disorder, withdrawal, tolerance, habituation, or misuse in sport- and exercise-related populations. PubMed, Web of Science Core Collection, and Scopus were searched from inception to 15 June 2026. Four studies met the eligibility criteria: one cross-sectional study of caffeine dependence in university sport students, two experimental withdrawal studies, and one historical analysis of caffeine use and misuse in competitive cyclists. The evidence suggests that questionnaire-assessed dependence-related features, anxiety, self-reported withdrawal symptoms, withdrawal status, habitual intake, and performance may be interconnected; however, the studies were heterogeneous and generally did not use diagnostic assessments of caffeine use disorder. Athlete-specific prevalence and risk factors therefore remain unknown. Current evidence is insufficient for firm clinical or epidemiological conclusions, but it identifies an important gap between widespread ergogenic caffeine use and limited research on loss of control, continued use despite harm, withdrawal-driven use, and functional impairment. Standardized, athlete-specific research is urgently needed.