['To investigate whether coinciding peak serum caffeine concentration with the onset of exercise enhances subsequent endurance performance.', 'Randomised, double-blind, crossover.', "In this randomised, placebo-controlled, double-blind crossover study, 14 male trained cyclists and triathletes (age 31±5year, body mass 75.4±5.7 kg, VO₂max 69.5±6.1 mL kg⁻¹ min⁻¹ and peak power output 417±35W, mean±SD) consumed 6 mg kg(-1) caffeine or a placebo either 1h (C(1h)) prior to completing a 40 km time trial or when the start of exercise coincided with individual peak serum caffeine concentrations (C(peak)). C(peak) was determined from a separate 'caffeine profiling' session that involved monitoring caffeine concentrations in the blood every 30 min over a 4h period.", 'Following caffeine ingestion, peak serum caffeine occurred 120 min in 12 participants and 150 min in 2 participants. Time to complete the 40 km time trial was significantly faster (2.0%; p=0.002) in C(1h) compared to placebo. No statistically significant improvement in performance was noted in the C(peak) trial versus placebo (1.1%; p=0.240). Whilst no differences in metabolic markers were found between C(peak) and placebo conditions, plasma concentrations of glucose (p=0.005), norepinephrine and epinephrine (p≤0.002) were higher in the C(1h) trial 6 min post-exercise versus placebo.'] Does coinciding exercise with peak serum caffeine improve cycling performance?