<p indent=0mm>Due to the high activity, excellent selectivity, mild reaction condition, and diverse function, biocatalysis has been recognized as a green tool for chemical synthesis. Especially with the progress in biotechnology (such as directed evolution and genetic engineering), it has become possible for biocatalysis to be an environmentally friendly alternative to traditional chemical synthesis processes. Redox reaction is an important category for the industrial application of biocatalysts. In enzymatic redox processes, oxidoreductases are driven to catalyze substrate conversion by consuming redox equivalents. To this end, it is a key issue to efficiently and economically supply redox equivalents for the enzymes. Photocatalysis has attracted much attention for its economic feasibility and environmental compatibility. As semiconductor photocatalysts that can utilize visible light are studied and developed, it can be expected to use clean, abundant, and sustainable solar energy to replace fossil fuel. Photoelectrochemical cells are a kind of configuration that can extract electrons from water by absorbing light energy (and electricity). The photogenerated electrons could be provided to biocatalysts in the form of reducing equivalents. Thus, by constructing photobioelectrochemical hybrid systems (hereafter noted as PBEC), the advantages of both photoelectrochemical and enzymatic catalysis could be combined, achieving a green process of continuous light-driven biotransformation. Microbes can be regarded as a “bag of enzymes” and are also widely studied in PBEC. Compared with enzymes, microbes have strong stability and good metabolic plasticity; however, the drawbacks are the requirement for continuous nutrition and energy supply, and relatively low specificity of products. PBEC has many practical bright sides. First, since the quasi-Fermi level of electrons can be adjusted by applying an external bias, water can be used to provide excited electrons, which means chemical electron donors (e.g., triethanolamine) are not required in such systems, avoiding side-product accumulation or side reactions. Second, the photocatalytic reaction and the biocatalytic one in a PBEC are generally compartmentalized into two chambers by a semi-permeable membrane. The electrons transfer through external wires, which connect the electrodes. Separating the anodic and cathodic reactions (i.e., water oxidation and biocatalytic reduction) can prevent the damage to biocatalysts or products caused by photogenerated oxidative holes or O<sub>2</sub> evolved from water splitting. In addition, the separation allows attempts to use various collocations of different photocatalysts and biocatalysts, as well as optimizations (such as buffer type, temperature, pH, illumination) in a single chamber without influencing the other one. Photoelectrodes and biocatalysts are two core functional components in a PBEC. The photoelectrode captures light energy and generates reducing equivalents, which are subsequently used by biocatalysts for bio-converting substrates to products. In this review, we summarize recent advances in this newly emerging field of PBEC. The first chapter discusses the principles and related studies for choosing photoelectrode materials. Biocatalysts employed in PBEC can be divided into two categories: enzymes and microbes. Based on different biocatalysts, representative works and some optimization strategies are introduced. Finally, prospects for future study and development of PBEC are given.