In this work, activated carbon fibers (ACFs) were plated with copper metal using electroless plating method and the effects of surface properties and pore structures on chromium adsorption properties were investigated. Surface properties of ACFs have been characterized using pH and acid/base values. BET data with N2 adsorption were used to obtain the structural parameters of ACFs. The electroless copper plating did significantly lead to a decrease in the surface acidity or to an increase in the surface basicity of ACFs. However, all of the samples possessed a well-developed micropore. The adsorption capacity of Cr(III) for the electroless Cu-plated ACFs was higher than that of the as-received, whereas the adsorption capacity of Cr(VI) for the former was lower than that of the latter. The adsorption rate constants (K1, K2, and K3) were also evaluated from chromium adsorption isotherms. It was found that K1 constant for Cr(III) adsorption depended largely on surface basicity. The increase of Cr(III) adsorption and the decrease of Cr(VI) adsorption were attributed to the formation of metal oxides on ACFs, resulting in increasing the surface basicity.