AbstractNovel methods for the preparation of metal‐supported materials are desired for better catalytic performance and selectivity. In this article, Ni supported on multiwall nanotubes (Ni/MWNTs) is synthesized with electrodeposition method for electrocatalytic CO2 reduction reaction (CO2RR). The sample drying time after electrodeposition is found critical to oxidize Ni for better activity, and higher Ni oxidation state is required for CO2RR. The loading effect study proves that higher current density is achieved from small Ni clusters than that from large nano particles. This work provides a pioneer approach to synthesize small Ni clusters using electrodeposition method for electrocatalytic CO2 conversion.