This study compared the effects of a single and divided dose of caffeine on endurance performance, post-exercise urinary caffeine and plasma paraxanthine concentrations. Nine male cyclists and triathletes, cycled for 90-min at 68%VO_2max, followed by a self-paced time-trial (work equivalent to 80%VO_2max workload over 30-min) with three randomised, balanced, and double-blind interventions: 1) placebo 60-min prior to, and 45-min into exercise (PP); 2) single caffeine dose (6 mg.kg^-1) 60-min prior to exercise and placebo 45-min into exercise (CP); and 3) divided caffeine dose (3 mg.kg^-1) 60-min prior to, and 45-min into exercise (CC). Time-trial performance was unchanged with caffeine ingestion (p = 0.08), but tended to be faster in the caffeine trials (CP: 24.2-min and CC: 23.4-min) compared with placebo (PP: 28.3-min). Post-exercise urinary caffeine concentration was significantly lower in CC (3.8 µg.ml^-1) compared to CP (6.8 µg.ml^-1). Plasma paraxanthine increased in a dose-dependent fashion and did not peak during exercise. In conclusion, dividing a caffeine dose provides no ergogenic effect over a bolus dose, but reduces post-exercise urinary concentration.