The effect of a cationic surfactant on the adsorption of Cr(VI) on activated carbon was investigated using cetylpyridinium chloride (CPC). At a concentration below the critical micelle concentration (CMC) of CPC, the adsorption of CPC and Cr(VI) reached equilibrium within 60 min, while it took 180 min at the concentration above CMC. CPC decreased the adsorption rate of Cr(VI) and increased the adsorption amount of Cr(VI) onto activated carbon. To analyze adsorption phenomena of Cr(VI), adsorption kinetic and isotherm were used and fitted well with the pseudo-second order kinetic model and Langmuir adsorption model, respectively. CPC introduced a cationic functional group on the surface of activated carbon and provided an adsorption site for Cr(VI).