Regulation　of　hydrogenation　capacity　in　cobalt-based　catalysts　is　crucial　for　the　effective　conversion　of　CO2　into　methanol.　Herein,　we　developed　a　cobalt　catalyst　supported　on　nitrogen-doped　carbon　(viz.,　Co-N/C),　specifically　enriched　with　pyridinic　N　bonding　to　the　cobalt　sites.　The　hydrogenation　capacity　of　the　Co-N/C　catalyst　was　carefully　tuned　by　controlling　the　arrangement　of　pyridinic　and　pyrrolic　N　dopants　through　the　ammonolysis　treatment　of　the　ZIF-67　precursor.　The　incorporation　of　pyridinic　N　significantly　reduces　electron　localization　around　the　cobalt　centers,　thereby　minimizing　unwanted　hydrogenation　to　methane.　The　optimized　Co-N/C　catalyst,　characterized　by　a　predominance　of　pyridinic　N,　achieved　a　turnover　frequency　of　47.8　h−1　for　methanol　production　under　2　MPa　pressure　and　180　°C　in　a　slurry　reactor,　surpassing　the　performance　of　a　conventional　Co/C　catalyst　featuring　pyrrolic　N　by　a　factor　of　seven.　Additionally,　the　Co-N/C　catalyst　exhibited　excellent　long-term　stability,　generating　70　mmol　of　CH3OH　and　only　1.5　mmol　of　CH4　over　five　cycles　(totaling　30　h).　Both　theoretical　and　experimental　investigations　revealed　that　pyridinic　N　has　a　greater　affinity　for　bonding　with　Co　compared　to　pyrrolic　and　graphitic　N,　and　the　pyridinic-N-cobalt　serves　as　active　sites　for　CO2　hydrogenation.　©　2024　Elsevier　B.V.