A copper-catalyzed hydrodechlorination of primary, secondary, and tertiary alkyl chlorides using diisobutylaluminum hydride is reported. This catalytic system offers a broad substrate scope, high yields, and good functional group tolerance. Mechanistic investigations indicated that the reaction predominantly proceeds via a radical pathway, as supported by radical clock experiments. Importantly, this study provides a new approach for the selective hydrodechlorination of unactivated alkyl chlorides and expands the utility of Cuhydride catalysis in sustainable chemical synthesis.