Photocatalysis holds the tantalizing potential to satisfy global energy demand, reduce greenhouse effect, and resolve environmental contamination. In particular, chemical transformation of biomass by sunlight has delivered a sustainable and decarbonized approach to the production of chemicals and fuels by using the abundant resources on earth. As the major byproduct in biodiesel processing, glycerol has introduced itself as a renewable, bio-derived feedstock for the production of value-added chemicals. To this end, the development of sunlight-driven “glycerochemistry” capable of transforming glycerol into high value-added chemicals has received much research attention over recent years. This Review summarizes the recent progress achieved in the realization of value-added chemical production from photocatalytic (PC) and photoelectrochmeical (PEC) glycerol oxidation. Spotlights are shined on the design of critical photoactive materials and the devising of reliable strategies that enable a rational control over the selectivity toward a desired product. Additionally, it addresses the current gaps in the interpretation of a veritable reaction mechanism both experimentally and theoretically. Lastly, current challenges and future prospects are pinpointed in order to accelerate the widespread deployment of PC and PEC glycerol valorization in academia and industries.

光催化在满足全球能源需求、减少温室效应和解决环境污染方面具有诱人的潜力。特别是，通过阳光对生物质进行化学转化，利用地球上丰富的资源，为化学品和燃料的生产提供了一种可持续和脱碳的方法。作为生物柴油加工过程中的主要副产品，甘油已成为一种可再生的生物衍生原料，用于生产增值化学品。为此，近年来，开发能够将甘油转化为高附加值化学品的阳光驱动的“甘油化学”受到了广泛的研究关注。本综述总结了光催化（PC）和光电化学（PEC）甘油氧化实现增值化学品生产的最新进展。焦点集中在关键光敏材料的设计和可靠策略的设计上，这些策略能够合理控制所需产品的选择性。此外，它还解决了当前在实验和理论上解释真正的反应机制方面的差距。最后，指出了当前的挑战和未来的前景，以加速 PC 和 PEC 甘油增值在学术界和工业界的广泛部署。