Rationale The cognitive and mood effects of caffeine are well documented. However, the majority of studies in this area involve caffeine-deprived, habitual caffeine users. It is therefore unclear whether any beneficial findings are due to the positive effects of caffeine or to the alleviation of caffeine withdrawal. Objectives The present placebo-controlled, double-blind, balanced crossover study investigated the acute cognitive and mood effects of caffeine in habitual users and habitual non-users of caffeine. Method Following overnight caffeine withdrawal, 24 habitual caffeine consumers (mean=217 mg/day) and 24 habitual non-consumers (20 mg/day) received a 150 ml drink containing either 75 or 150 mg of caffeine or a matching placebo, at intervals of 48 h. Cognitive and mood assessments were undertaken at baseline and 30 min post-drink. These included the Cognitive Drug Research computerised test battery, two serial subtraction tasks, a sentence verification task and subjective visual analogue mood scales. Results There were no baseline differences between the groups mood or performance. Following caffeine, there were significant improvements in simple reaction time, digit vigilance reaction time, numeric working memory reaction time and sentence verification accuracy, irrespective of group. Self-rated mental fatigue was reduced and ratings of alertness were significantly improved by caffeine independent of group. There were also group effects for rapid visual information processing false alarms and spatial memory accuracy with habitual consumers outperforming non-consumers. There was a single significant interaction of group and treatment effects on jittery ratings. Separate analyses of each groups responses to caffeine revealed overlapping but differential responses to caffeine. Caffeine tended to benefit consumers mood more while improving performance more in the non-consumers. Conclusions These results do not support a withdrawal alleviation model. Differences in the patterns of responses to caffeine by habitual consumers and habitual non-consumers may go some way to explaining why some individuals become caffeine consumers.