Catalytic hydrodechlorination of carbon tetrachloride (CCl4) is an effective measure to remove CCl4 due to its pollutant character. The dechlorination of CCl4 to dichloromethane (CH2Cl2) and chloroform (CHCl3) with a molar ratio of 3:2 was catalyzed by carbon-supported silver (Ag/C) catalyst in methanol solution. It was proposed from the catalytic results and characterization (X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy) data that, the chloride ion is abstracted from adsorbed CCl4 by Ag to form CCl3 and CCl2 radicals and silver chloride (AgCl), and meanwhile the dehydrogenation of methanol over Ag domains intrigues initial active Ag H species and formaldehyde (HCHO); then the CCl3 and CCl2 radicals are combined with Ag-H to generate reaction products (CHCl3 and CH2Cl2) and Ag, and the dehydrogenated product HCHO facilitates the regeneration of formed AgCl to Ag with formation of carbon monoxide and hydrogen chloride. The catalyst can be recovered and recycled, and there was no significant decrease in catalytic activity and selectivity after 4th recycling.