With the ever-rising concentration of CO? in the atmosphere, now above 420 ppm, there is an urgent need for advanced technology to enable sustainable carbon utilization. Photochemical reduction of CO? provides a promising approach towards the valorization of this greenhouse gas by converting it into valuable chemicals and fuel via solar energy. This paper aims to present an overview of the fundamental principles of the photochemical CO? conversion process and approaches for designing efficient catalysts and optimizing its performance. In our analysis, we focus on semiconductor-based photocatalysis, the use of metal-organic frameworks (MOFs) for the selective reduction of CO? into C? products (CO, CH?, HCOOH, CH?OH) and C?? products (C?H?, C?H?OH). On the basis of the quantitative analysis of reaction pathways and thermodynamics of the process, we conclude that surface-treated TiO? produces 85.6 µmol · g?¹· h?¹ CO with selectivity up to 92.3%, whereas MOF-based catalysts can reach conversion rates of more than 99% CH? with 7.5 mmol · g?¹ · h?¹ production.