As a naturally occurring and stable energy supply, biomass will be the leading renewable energy in the future, and its high-value application will help promote the realization of carbon neutrality. Glucose, as the basic unit of lignocellulosic biomass, has been widely investigated as the feedstock to produce various value-added chemicals. Compared to the traditional glucose valorization platforms, such as thermal catalysis and biological fermentation, solar-driven photocatalysis holds the advantages in mild reaction conditions and controllable reaction kinetics, and it is emerging as a sustainable and efficient technology for glucose conversion. With the rational design of the photocatalysts, glucose could be selectively converted into specified chemicals via oriented bond cleavage along with the sustainable generation of hydrogen at the same time, which is the so-called glucose photorefinery process. This present review introduces the general principles and latest progress in glucose photorefinery. The rational design of bifunctional photocatalysts to achieve extended light absorption, efficient charge separation, and favorable surface reaction is also introduced. The oriented breakage of the chemical bonds in glucose molecules to produce different chemicals on different active sites is highlighted. Finally, challenges and perspectives on glucose photorefinery to achieve further efficiency and more fruitful reaction pathways are proposed. This present review is believed to provide guidance for the biomass valorization by mild photocatalysis to simultaneously produce sustainable fuels and chemicals with the rational design of dually functional photocatalysts.