Both carbohydrate (CHO) and caffeine have been used as ergogenic aids during exercise. It has been suggested that caffeine increases intestinal glucose absorption, but there are also suggestions that it may decrease muscle glucose uptake. The purpose of the study was to investigate the effect of caffeine on exogenous CHO oxidation. In a randomized crossover design, eight male cyclists (age 27 ± 2 yr, body mass 71.2 ± 2.3 kg, maximal oxygen uptake 65.7 ± 2.2 ml·kg−1·min−1) exercised at 64 ± 3% of maximal oxygen uptake for 120 min on three occasions. During exercise subjects ingested either a 5.8% glucose solution (Glu; 48 g/h), glucose with caffeine (Glu+Caf, 48 g/h + 5 mg·kg−1·h−1), or plain water (Wat). The glucose solution contained trace amounts of [U-13C]glucose so that exogenous CHO oxidation could be calculated. CHO and fat oxidation were measured by indirect calorimetry, and13C appearance in the expired gases was measured by continuous-flow IRMS. Average exogenous CHO oxidation over the 90- to 120-min period was 26% higher ( P < 0.05) in Glu+Caf (0.72 ± 0.04 g/min) compared with Glu (0.57 ± 0.04 g/min). Total CHO oxidation rates were higher ( P < 0.05) in the CHO ingestion trials compared with Wat, but they were highest when Glu+Caf was ingested (1.21 ± 0.37, 1.84 ± 0.14, and 2.47 ± 0.23 g/min for Wat, Glu, and Glu+Caf, respectively; P < 0.05). There was also a trend ( P = 0.082) toward an increased endogenous CHO oxidation with Glu+Caf (1.81 ± 0.22 g/min vs. 1.27 ± 0.13 g/min for Glu and 1.12 ± 0.37 g/min for Wat). In conclusion, compared with glucose alone, 5 mg·kg−1·h−1of caffeine coingested with glucose increases exogenous CHO oxidation, possibly as a result of an enhanced intestinal absorption.