Photosensitized heterogeneous CO₂ reduction (PHCR) has emerged as a promising means to convert CO₂ into valuable chemicals, however, challenged by the relatively low carbonaceous product selectivity caused by the competing hydrogen evolution reaction (HER). Here, we report a PHCR system that couples Ru(bpy)₃²⁺ photosensitizer with {001} faceted LiCoO₂ nanosheets photocatalyst to simultaneously yield 21.2 and 722 μmol·g⁻¹·h⁻¹ of CO, and 4.42 and 108 μmol·g⁻¹·h⁻¹ of CH₄ under the visible light and the simulated sunlight irradiations, respectively, with completely suppressed HER. The experimental and theoretical studies reveal that the favored CO₂ adsorption on the exposed Li sites on {001} faceted LiCoO₂ surface is responsible for the completely suppressed HER.