The reductive dechlorination of 2,4,6-trichlorophenol (2,4,6-TCP) was studied using zero-valent metals (ZVMs) and bimetals. A reliable extraction method was required to distinguish the removal by chemical transformation from the removal by physical adsorption on the ZVMs or bimetal. Three liquid-liquid extraction methods with ethyl acetate were evaluated by conducting mass recovery tests in the ZVM-chlorophenol systems. A typical liquid-liquid extraction showed low recoveries for 2,4,6-TCP and the reaction products while the modified liquid-liquid extraction involving acid addition gave increased recoveries. The Mg system needed an additional modification since the modified extraction method was not working on the Mg and Pd/Mg system. Pd/Fe and Pd/Zn gave the highest reaction rate for 2,4,6-TCP dechlorination, producing less or no chlorinated daughter compounds while the plain metals such as Fe and Zn showed much slower degradation rates for 2,4,6-TCP.