Photoelectrochemical reduction of CO₂ is a promising approach for renewable fuel production. We herein report a novel strategy for preparation of hybrid photocathodes by immobilizing molecular cobalt catalysts on TiO2-protected n+-p Si electrodes (Si|TiO₂) coated with multiwalled carbon nanotubes (CNTs) by π–π stacking. Upon loading a composite of Co^II(BrqPy) (BrqPy=4′,4′′-bis(4-bromophenyl)-2,2′ : 6′,2′′ : 6′′,2′′′-quaterpyridine) catalyst and CNT on Si|TiO₂, a stable 1-Sun photocurrent density of −1.5 mA cm⁻² was sustained over 2 h in a neutral aqueous solution with unity Faradaic efficiency and selectivity for CO production at a bias of zero overpotential (−0.11 V vs. RHE), associated with a turnover frequency (TOF_CO) of 2.7 s⁻¹. Extending the photoelectrocatalysis to 10 h, a remarkable turnover number (TON_CO) of 57000 was obtained. The high performance shown here is substantially improved from the previously reported photocathodes relying on covalently anchored catalysts.