Co nanoparticles (NPs) encapsulated in N‐doped carbon nanotubes (Co@NC900) are systematically investigated as a potential alternative to precious Pt‐group catalysts for hydrogenative heterocyclization reactions. Co@NC900 can efficiently catalyze hydrogenative coupling of 2‐nitroaniline to benzaldehyde for synthesis of 2‐phenyl‐1H‐benzo[d]imidazole with >99 % yield at ambient temperature in one step. The robust Co@NC900 catalyst can be easily recovered by an external magnetic field after the reaction and readily recycled for at least six times without any evident decrease in activity. Kinetic experiments indicate that Co@NC900‐promoted hydrogenation is the rate‐determining step with a total apparent activation energy of 41±1 kJ mol−1. Theoretical investigations further reveal that Co@NC900 can activate both H2 and the nitro group of 2‐nitroaniline. The observed energy barrier for H2 dissociation is only 2.70 eV in the rate‐determining step, owing to the presence of confined Co NPs in Co@NC900. Potential industrial application of the earth‐abundant and non‐noble transition metal catalysts is also explored for green and efficient synthesis of heterocyclic compounds.