Hybridization of homogeneous catalytic sites with a photoelectrode is an attractive approach to highly selective and tunable photocatalysis using heterogeneous platforms. However, weak and unclear surface chemistry often leads to the dissociation and irregular orientation of catalytic centers, restricting long-term usability with high selectivity. Well-defined and robust ligands that can persist under harsh photocatalytic conditions are essential for the success of hybrid-type photocatalysis. Here, we introduce N-heterocyclic carbene as a durable linker for the immobilization of a Rubpy complex-based CO2 reduction site (cis-dichloro-(4,4'-diphosphonato-Rubpy)(p-cymene) (RuCY)) on a p-type gallium nitride/gold nanoparticle (p-GaN/AuNP) heterostructure. The p-GaN/AuNPs/RuCY photocathode was coupled with a hematite photoanode to drive photoelectrochemical CO2 reduction along with water oxidation. Highly selective CO2 reduction into formates, up to 98.2%, was achieved utilizing plasmonic hot electrons accumulated on AuNPs. The turnover frequency was 1.46 min(-1) with a faradic efficiency of 96.8% under visible light illumination (243 mW.cm(-2)). This work demonstrates that the N-heterocyclic carbene-mediated surface functionalization with homogeneous catalytic sites is a promising approach to increase the sustainability and usability of hybrid catalysts.