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Caffeine (CAF) is widely consumed across sport and exercise for its reputed ergogenic properties, including central nervous stimulation and enhanced muscular force development. However, expectancy and the related psychological permutations that are associated with oral CAF ingestion are generally not considered in most experimental designs and these could be important in understanding if/how CAF elicits an ergogenic effect. The present paper reviews 17 intervention studies across sport, exercise, and cognitive performance. All explore CAF expectancies, in conjunction with/without CAF pharmacology. Thirteen out of 17 studies indicated expectancy effects of varying magnitudes across a range of exercise tasks and cognitive skills inclusive off but not limited to; endurance capacity, weightlifting performance, simple reaction time and memory. Factors, such as motivation, belief, and habitual CAF consumption habits influenced the response. In many instances, these effects were comparable to CAF pharmacology. Given these findings and the lack of consistency in the experimental design, future research acknowledging factors, such as habitual CAF consumption habits, habituated expectations, and the importance of subjective post-hoc analysis will help to advance knowledge within this area.