A new type of combined heterogeneous catalyst, PVP-PdCl2-CuCl2/SiO2-PEG600, was prepared by reaction of silica gel functionalized by polyethylene glycol (PEG) with average molecular weight 600 as a carrier system with phase transfer properties, with polyvinylpyrrolidone (PVP)-anchored PdCl2 and CuCl2 complex, and characterized by IR, XPS and TEM. The catalyst, in which the Pd/Cu molar ratio is 2/1, has shown good activity and selectivity for dechlorination of aromatic chlorides in water. In the presence of HCOONa as hydrogen donor and basic media, conversion in the dechlorination of p-chlorotoluene can reach 96.6% at 80 degreesC only for 2.5 h.