The objectives of this study were to estimate the impact of chewing time on caffeine release from gum and to understand caffeine pharmacokinetics. Caffeine release increased with chewing time (2 min < 5 min < 10 min). Furthermore, two plasma caffeine concentration peaks were observed suggesting that caffeine absorption occurs both through the oral mucosa and gastrointestinal tract. This is of practical relevance to maximise caffeine doses and to synchronise effort with peak caffeine concentration.