The selective activation of CCl bonds of hydrochlorofluoromethanes and chloromethanes at moderate reaction conditions using ACF in a combination with Et3GeH is presented. The reactions of the chloromethanes (CH3Cl, CH2Cl2, CHCl3 and CCl4) in the presence of Et3GeH and ACF as catalyst led to the activation of only one CCl bond resulting in the hydrodechlorination. Friedel-Crafts reactions with benzene as solvent are suppressed by Et3GeH. A selective hydrodechlorination of hydrochlorofluoromethanes was achieved, because a transformation of a CF bond into a CH bond by the combination of ACF with Et3GeH did not occur. Supporting PulseTA® experiments illustrated the interaction between the solid catalyst and Et3GeH, the solvent benzene or CH2Cl2. Display omitted •Selective monohydrodechlorination reactions of polychlorinated alkanes were achieved.•Hydrodechlorination of CHCl2F and CHClF2 occurs with selectivity towards C−Cl activation.•Heterogeneous catalytic reactions were developed.•PTA studies give information about the interaction between the substrates at ACF · Et3GeH.