The ergogenic effects of acute caffeine intake on endurance cycling performance lasting ~1 h have been well documented in controlled laboratory studies. However, the potential benefits of caffeine supplementation in cycling disciplines such as cross-country/mountain biking have been rarely studied. In cross-country cycling, performance is dependent on endurance capacity, which may be enhanced by caffeine, but also on the technical ability of the cyclist to overcome the obstacles of the course. So, it is possible that the potential benefits of caffeine are not translated to cross-country cycling. The main objective of this study was to investigate the effects of acute caffeine intake, in the form of coffee, on endurance performance during a cross-country cycling time trial. Eleven recreational cross-country cyclists (mean ± SD: age: 22 ± 3 years; nine males and two females) participated in a single-blinded, randomised, counterbalanced and crossover experiment. After familiarisation with the cross-country course, participants completed two identical experimental trials after the ingestion of: (a) 3.00 mg/kg of caffeine in the form of soluble coffee or (b) 0.04 mg/kg of caffeine in the form of decaffeinated soluble coffee as a placebo. Drinks were ingested 60 min before performing a 13.90 km cross-country time trial over a course with eight sectors of varying technical difficulty. The time to complete the trial and the mean and the maximum speed were measured through Global Positioning System (GPS) technology. Heart rate was obtained through a heart rate monitor. At the end of the time trial, participants indicated their perceived level of fatigue using the traditional Borg scale. In comparison to the placebo, caffeine intake in the form of coffee significantly reduced the time to complete the trial by 4.93 ± 4.39% (43.20 ± 7.35 vs. 41.17 ± 6.18 min; p = 0.011; effect size [ES] = 0.300). Caffeine intake reduced the time to complete four out of eight sectors with different categories of technical difficulty (p ≤ 0.010; ES = 0.386 to 0.701). Mean heart rate was higher with caffeine (169 ± 6 vs. 162 ± 13 bpm; p = 0.046; ES = 0.788) but the rating of perceived exertion at the end of the trial was similar with caffeinated coffee than with the placebo (16 ± 1 vs. 16 ± 2 a.u.; p = 0.676; ES = 0.061). In conclusion, the intake of 3 mg/kg of caffeine delivered via soluble coffee reduced the time to complete a cross-country cycling trial in recreational cyclists. These results suggest that caffeine ingested as coffee may be an ergogenic substance for cross-country cycling.