This review focuses on the advancements and challenges in photoelectrochemical (PEC) catalysis for the synthesis of high-value chemicals from sustainable precursors. PEC catalysis offers a promising avenue for producing value-added chemicals and consumables from renewable resources, addressing the energy and environmental crises associated with fossil fuel use. The review covers the fundamentals of PEC reactions, common photoelectrode fabrication methods, recent progress in PEC conversion of various feedstocks, and the challenges and prospects in the field. Key topics include the evaluation of PEC reactions, the geometry of light illumination, efficiency metrics, and product analysis. The review also discusses the fabrication methods for photoelectrodes, such as drop casting, spin coating, doctor blade, finger rubbing, particle transfer, vacuum filter transfer, spray pyrolysis, electrochemical deposition, hydrothermal/solvothermal methods, and chemical vapor deposition. The aim is to facilitate further development of PEC technology for upgrading renewable precursors to valuable products and pharmaceuticals.This review focuses on the advancements and challenges in photoelectrochemical (PEC) catalysis for the synthesis of high-value chemicals from sustainable precursors. PEC catalysis offers a promising avenue for producing value-added chemicals and consumables from renewable resources, addressing the energy and environmental crises associated with fossil fuel use. The review covers the fundamentals of PEC reactions, common photoelectrode fabrication methods, recent progress in PEC conversion of various feedstocks, and the challenges and prospects in the field. Key topics include the evaluation of PEC reactions, the geometry of light illumination, efficiency metrics, and product analysis. The review also discusses the fabrication methods for photoelectrodes, such as drop casting, spin coating, doctor blade, finger rubbing, particle transfer, vacuum filter transfer, spray pyrolysis, electrochemical deposition, hydrothermal/solvothermal methods, and chemical vapor deposition. The aim is to facilitate further development of PEC technology for upgrading renewable precursors to valuable products and pharmaceuticals.