In order to enhance the Fenton oxidation of 2,4,6-trichlorophenol, copper ion was introduced to the Fenton reaction. The results show that, differing from ferrous ion, the copper ion exhibits no capability to decompose hydrogen peroxide to degrade the organic substrates; however, it can accelerate the degradation rate of 2,4,6-trichlorophenol by Fenton reaction, enhance the decomposition of hydrogen peroxide, increase the removal efficiency of TOC and release of chloride ion. Even lower copper ion dosage have significant enhancement on the degradation. The result of complete inhibition of the reaction by methanol and tert-Butanol suggests that hydroxyl radical is the most important reactive species in the Cu2+ enhanced Fenton reaction.