The purpose of the present study was to examine the effect of ad libitum ingestion of a carbohydrate-electrolyte solution (CES) with 150 mg x L (-1) caffeine (CAF) on urinary CAF concentration after 4 h of endurance exercise. Fifty-eight healthy and well-trained male subjects ingested ad libitum a 7 % CES with 150 mg x L (-1) CAF during 4 h cycling at 50 % of maximal work capacity. Total fluid consumption (mean +/- SE) was 2799 +/- 72 mL and CAF intake was 420 +/- 11 mg (5.7 +/- 0.2 mg x kg (-1) body weight). The post-exercise urinary CAF concentration (4.53 +/- 0.25 microg x mL (-1)) was below the doping level of the International Olympic Committee (12 microg x mL (-1)) in all subjects (range 1.20 - 10.84 microg x mL (-1)). A highly positive correlation was observed between CAF intake and post-exercise urinary CAF concentration (r = 0.68, p < 0.001). It is concluded that ad libitum ingestion of a CES with 150 mg x L (-1) CAF during 4 h cycling resulted in post-exercise urinary concentration below the doping level in all subjects.