Caffeine consumption and cigarette smoking tend to occur within the same individuals and at the same time. One potential explanation for this co-use is that caffeine consumption increases subjective smoking reinforcement. Electronic diaries were used to collect momentary reports of smoking, caffeine consumption, temptation/urge to smoke, and subjective smoking reinforcement in 74 prequit smokers. Momentary reports of caffeine consumption and smoking were associated, replicating previous findings. These results remained significant when contextual factors (time of day, weekday/weekend, presence of others, presence of others smoking, location, and past hour alcohol consumption) were covaried. Caffeine consumption was also associated with positive cigarette appraisals and reports of strong temptation/urge to smoke and urge reduction from the prior cigarette. Under the conditions of caffeine consumption versus at other times, smokers were significantly more likely to report their last cigarette as producing a rush/buzz, being pleasant, relaxing, and tasting good. The effects for temptation/urge to smoke and rush/buzz varied as a function of latency since smoking. Caffeine consumption increased reports of urge to smoke and rush/buzz only when smoking occurred more than 15 minutes prior to the diary entry. Findings suggest that caffeine consumption influences some aspects of smoking motivation or affects memorial processing of smoking reinforcement.