In the direct synthesis of phenylchlorogermanes, copper(l) chloride was the best catalyst among the metal chlorides tested, the products being diphenyldichlorogermane and phenyltrichlorogermane. The reaction mainly gave diphenyldichlorogermane; however at the beginning of the reaction, phenyltrichlorogermane was afforded by the reaction of chlorobenzene and dichlorogermylene formed from metallic germanium and chloride ion in the catalyst.