Pyrolysis has the potential of transforming waste into valuable recyclable products. Pyrolytic char(PC) is one of the most important products from the pyrolysis of used tires. One of the most significant applications for pyrolytic char recovered is used for the removal of Cr(Ⅵ) in the wastewater effluent to control waste by waste. The surface chemistry properties of surface element distribution / concentration and chemical structure were examined for the pyrolytic char and the commercial activated carbon(CAC) respectively. The results showed that surfaces of PC possesses a large amount of ester and hydrocarbon graft, whereas there are mainly carbon functional components of C-OH, C=O and COOH on the surface of CAC. Therefore the surface electronegativity of PC is lower than that of CAC in the water. The repulsive interactions between the surfaces of PC and the negatively charged Cr(Ⅵ) ion are weaker than that of CAC, which results in an intensification of the adsorption process by the utilization of PC. The adsorption isotherms of Cr(Ⅵ) ion on the two kinds of carbons were determined experimentally. The larger adsorption amount on the PC in the case of Cr(Ⅵ) may be attributed mainly to its special surface micro-chemical environment. The mechanism of the removal Cr(Ⅵ) from aqueous solution was assumed to be the integration of adsorption and redox reaction. The adsorption was the rate-controlled step for Cr(Ⅵ) removal. The adsorption of Cr(Ⅵ) has been identified as pseudo-second- order kinetics. The rate constants of adsorption have been evaluated.