Benzimidazole derivatives have wide-spectrum biological activities and pharmacological effects, but remain challenging to be produced from biomass feedstocks. Here, we report a green hydrogen transfer strategy for the efficient one-pot production of benzimidazoles from a wide range of bio-alcohols and o-nitroanilines enabled by cobalt nitride species on hierarchically porous and recyclable nitrogen-doped carbon catalysts (Co/CN_x-T, T denotes the pyrolysis temperature) without using an external hydrogen source and base additive. Among the tested catalysts, Co/CN_x-700 exhibited superior catalytic performance, furnishing 2-substituted benzimidazoles in 65%–92% yields. Detailed mechanistic studies manifest that the coordination between Co²⁺ and N with appropriate electronic state on the porous nitrogen-doped carbon having structural defects, as well as the remarkable synergetic effect of Co/N dual sites contribute to the pronounced activity of Co/CN_x-700, while too high pyrolysis temperature may cause the breakage of the catalyst Co–N bond to lower down its activity. Also, it is revealed that the initial dehydrogenation of bio-alcohol and the subsequent cyclodehydrogenation are closely correlated with the hydrogenation of nitro groups. The catalytic hydrogen transfer-coupling protocol opens a new avenue for the synthesis of N-heterocyclic compounds from biomass.