A novel method for the synthesis of benzyl chlorides and diarylmethanes from methylarenes and CCl4 in the presence of nitrile-activated catalysts based on the Mn(acac)(3) and Mo(CO)(6) complexes was developed. The reaction proceeds through the chlorination of one of the methyl groups in methylarenes by carbon tetrachloride to form the corresponding benzyl chlorides, which then alkylate in situ the starting methylarenes to diarylmethanes via the Friedel-Crafts reaction. The reaction is common for the entire methylarene series, including toluene, para-, meta-, and ortho-xylenes, pseudocumene, and durene. The effects of the central atom and its ligand environment in the catalyst and of the reaction conditions on the yield of benzyl chlorides and diarylmethanes were studied.