The present study had two main aims. The first was to examine associations between psychosocial factors, health-related behaviours, regular level of caffeine consumption, time of day and levels of caffeine in saliva following acute caffeine challenges. The second aim was to determine whether individual differences in changes in performance following ingestion of caffeine were related to levels of caffeine in saliva. One hundred and forty-four young adults participated in the study. Questionnaires were administered prior to the study to measure psychosocial characteristics, health-related behaviours and habitual levels of caffeine consumption. Two double-blind acute caffeine challenges were then carried out 1 week apart. Volunteers were given either placebo or 1.5 or 3 mg/kg of caffeine on each occasion. The challenges were carried out at 8 : 00, 11 : 00, 14 : 00 or 18 : 00 h so that the impact of time of day could be assessed. In the week between the two challenges the volunteers consumed either caffeinated or decaffeinated products. This allowed investigation of the effects of caffeine withdrawal on caffeine metabolism. Prior to each caffeine challenge volunteers performed a range of tasks, and a baseline saliva sample was taken. The tasks were repeated 1 h after ingestion of the caffeine, with saliva samples being taken at the start and end of the 1 h test battery. The results showed that the level of caffeine in the saliva was a good indicator of the dose of caffeine consumed and of compliance with the withdrawal manipulation. Caffeine levels were not influenced by time of day, habitual caffeine consumption, psychosocial factors or health-related behaviours. Individual differences in caffeine levels in saliva were not related to the individual variation in the effects of caffeine on performance. Copyright 2001 John Wiley & Sons, Ltd.