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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 CoII(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 (TOFCO) of 2.7 s−1. Extending the photoelectrocatalysis to 10 h, a remarkable turnover number (TONCO) of 57000 was obtained. The high performance shown here is substantially improved from the previously reported photocathodes relying on covalently anchored catalysts. [ABSTRACT FROM AUTHOR]