Caffeine is the world’s most commonly used stimulant of the central nervous system. Caffeine is present in coffee and other beverages such as tea, soft drinks, and cocoa-based foods. The caffeine expectancy questionnaire was developed to investigate the effects of caffeine expectations and thus contribute to knowledge about its usage and subjective effects (response expectancies). This study aimed to evaluate caffeine expectation psychometrically in a sample of the Brazilian population. The original version of the “Caffeine Expectancy Questionnaire (CaffEQ)” was translated and validated into Brazilian-Portuguese and adapted to Brazilian culture to be used in the Brazilian adult (19–59 y) population. After the translation and back-translation processes of the original CaffEQ questionnaire, the content and semantic validation were performed by a group of experts. The Brazilian-Portuguese version of the questionnaire consists of 47 items, in seven factors, which assess subjective perceptions about the effects of caffeine. Interobserver reproducibility and internal consistency of the questionnaire were tested with a convenience sample (n = 50) of Brazilian adult consumers of caffeine sources, who completed the Brazilian CaffEQ (CaffEQ-BR) on two occasions separated by 24 h. All of the 47 questions were adequate regarding reliability, clarity, and comprehension. Psychometric properties could be replicated consistently. Appropriate internal consistency and validation were confirmed by Cronbach’s alpha (α) 0.948, and an intraclass correlation coefficient of 0.976 was observed. The CaffEQ-BR was applied using a web-based platform to a convenience sample of Brazilian adults from all 27 Brazilian states (n = 4202 participants), along with measures of sociodemographic and caffeine consumption data. Factor validity was verified by confirmatory factor analysis. The seven factors presented a good fit for Root Mean Square Error of Approximation—RMSEA = 0.0332 (95% CI: 0.0290–0.0375). By confirming the validity and reliability of CaffEQ-BR, a useful tool is now available to assess caffeine expectations in the Brazilian adult population.