Efficient and selective photocatalytic CO2 reduction was obtained within a hybrid system that is formed in situ via a Schiff base condensation between a molecular iron quaterpyridine complex bearing an aldehyde function and carbon nitride. Irradiation (blue LED) of an CH3CN solution containing 1,3‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1H‐benzo[d]imidazole (BIH), triethylamine (TEA), Feqpy‐BA (qpy‐BA=4‐([2,2′:6′,2′′:6′′,2′′′‐quaterpyridin]‐4‐yl)benzaldehyde) and C3N4 resulted in CO evolution with a turnover number of 2554 and 95 % selectivity. This hybrid catalytic system unlocks covalent linkage of molecular catalysts with semiconductor photosensitizers via Schiff base reaction for high‐efficiency photocatalytic reduction of CO2, opening a pathway for diverse photocatalysis.