The purpose of this study was to determine the most efficacious time to administer caffeine (CAF) in chewing gum to enhance cycling performance. Eight male cyclists participated in 5 separate laboratory sessions. During the first visit, the subjects underwent a graded exercise test to determine maximal oxygen consumption (V[Combining Dot Above]O(2)max). During the next 4 visits, 3 pieces of chewing gum were administered at 3 time points (120-minute precycling, 60-minute precycling, and 5-minute precycling). In 3 of the 4 visits, at 1 of the time points mentioned previously, 300 mg of CAF was administered. During the fourth visit, placebo gum was administered at all 3 time points. The experimental trials were defined as follows: trial A (-120), trial B (-60), trial C (-5), and trial D (Placebo). After baseline measurements, time allotted for gum administration, and a standard warm-up, the participants cycled at 75% V[Combining Dot Above]O(2)max for 15 minutes then completed a 7-kJ·kg(-1) cycling time trial. Data were analyzed using a repeated measures analysis of variance. Cycling performance was improved in trial C (-5), but not in trial A (-120) or trial B (-60), relative to trial D (Placebo). CAF administered in chewing gum enhanced cycling performance when administered immediately prior, but not when administered 1 or 2 hours before cycling.