Gallic acid (GA) is a naturally occurring plant polyphenol compound. Experiments were conducted to study the kinetics and effects of pH, temperature, irradiation, and initial hexavalent chromium (Cr(VI)) concentration on Cr(VI) reduction by GA. Results indicated that Cr(VI) could be reduced to chromium oxide (Cr(III)) with GA in a wide range of pH values from 2.0 to 8.5. The reaction followed a pseudo-first-order kinetic model with respect to Cr(VI) and GA in acid conditions (pH 2.0–5.0). However, the reaction did not follow the pseudo-first-order kinetic model at pH 6.5 and 8.5. Removal efficiencies and reaction rate constants of Cr(VI) significantly increased with decreasing pH value and increasing temperature. The effect of irradiation on Cr(VI) reduction increased with increasing pH, and irradiation improved the removal efficiency of Cr(VI) by 11.29% at pH 6.5. At pH 2.0, nearly all molar ratios of GA required for the reduction of Cr(VI) were 1:2 (±0.1) under different initial Cr(VI) concentrations; however, the molar ratios of GA required for the reduction of Cr(VI) were 1:1.29, 1:1.43, and 1:1.69, respectively, when the initial Cr(VI) concentrations were 10, 25, and 50 mg/L at pH 5.5.