Developing high‐performance heterogeneous catalysts for one‐pot reductive amination reactions is critically important for pharmaceutical and agrochemical synthetic industries. In this work, N‐doped carbon nanotubes supported CoPt alloy decorated Co nanoparticles (NPs) are successfully fabricated. As a consequence, the resultant catalyst exhibits desirable activity, selectivity and stability toward the one‐pot synthesis of imines. More importantly, the extensive experimental studies and density function theory (DFT) calculations results reveal that the high catalytic activity of the catalyst is mainly due to the co‐existence of CoPt alloy NPs and Co NPs with Co−Nx active sites. The high selectivity of imines could be ascribed to the following aspects: (1) competitively preferred adsorption of nitroarenes to avoid side‐hydrogenation of aldehydes; (2) weakened adsorption of imines to minimize its over‐hydrogenation. This work may provide a promising direction and strategy to design high‐performance reductive amination catalysts for industrial applications.