Pyridinium has been shown to be a cocatalyst for the electrochemical reduction of CO2 on metal and semiconductor electrodes, but its exact role has been difficult to elucidate. In this work, we create cooperative cobalt-protoporphyrin (CoPP) and pyridine/pyridinium (py/pyH(+)) catalytic sites on metal-organic layers (MOLs) for an electrocatalytic CO2 reduction reaction (CO2RR). Constructed from [Hf-6(mu(3)-O)(4)(mu(3)-OH)(4)(HCO2)(6)] secondary building units (SBUs) and terpyridine-based tricarboxylate ligands, the MOL was postsynthetically functionalized with CoPP via carboxylate exchange with formate capping groups. The CoPP group and the pyridinium (pyH(+)) moiety on the MOL coactivate CO2 by forming the [pyH(+)--O2C-CoPP] adduct, which enhances the CO2RR and suppresses hydrogen evolution to afford a high CO/H-2 selectivity of 11.8. Cooperative stabilization of the [pyH(+)--O2C-CoPP] intermediate led to a catalytic current density of 1314 mA/mgCo for CO production at -0.86 V-RHE, which corresponds to a turnover frequency of 0.4 s(-1).