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Caffeine mouth rinsing (CAF-MR) has been shown to improve reaction time (RT). CAF-MR studies have generally used 1.2% CAF concentrations, but the effect of using different concentrations is unknown. Therefore, we compared the effect of different concentrations of CAF-MR on RT. Forty-five trained male athletes (age: 18 ± 3 y) volunteered to participate in this double-blind, randomized controlled crossover study. Participants completed five testing sessions (Control, Placebo (water)-MR, and 1.2%, 1.8%, and 2.4% CAF-MR), with hand and foot RTs assessed immediately after MR. All CAF-MR conditions resulted in significantly faster hand and foot RT compared to Control and Placebo (all p < 0.001, except for foot RT with 1.8% CAF-MR vs. Placebo: NS). For both hand and foot RT, 1.2% and 1.8% CAF-MR did not significantly differ, but RT for 2.4% CAF-MR was significantly faster than both (p < 0.001). Improvements in RT for 2.4% CAF-MR vs. Placebo were 22% for hand RT and 21% for foot RT. In conclusion, these findings demonstrate that higher CAF-MR concentrations than those typically used can result in greater improvements in RT. This has implications for the practical use of CAF-MR to enhance performance in sports in which optimal RT is a factor of success.