Abstract Photocatalytic CO 2 reduction to CH 3 OH, particularly with metal‐organic frameworks (MOFs) as photocatalysts, has garnered significant attention due to its long‐term potential to harness sunlight for converting CO 2 into a valuable fuel and chemical feedstock. Numerous studies in the literature report the successful formation of CH 3 OH from photocatalytic CO 2 reduction, sometimes supplemented with sacrificial agents, with claims substantiated by isotopic labelling measurements. However, in this Scientific Perspective, we note that much of the existing evidence has not been obtained under sufficiently rigorous experimental conditions to conclusively confirm the formation of a highly reactive product like CH 3 OH from the chemically stable CO 2 molecule. This Scientific Perspective outlines best practices designed to provide robust evidence for CH 3 OH formation in photocatalytic processes, which could be instrumental in clarifying the state‐of‐the‐art and accelerating the development of this technology toward practical applications.