Photoelectrotrophic metabolism (photoelectrotrophy) is an emerging energy-conversion mode in which non-photosynthetic microorganisms harvest light-derived electrons from photosensitizers (e.g., semiconductor minerals and natural organic matter) to fuel intracellular redox reactions and support growth. This concept broadens microbial energy acquisition beyond classical phototrophy and chemotrophy. However, it is still not fully understood how environmental conditions, metabolic pathways, and environmental geochemical factors affect photoelectrotrophic metabolism in microorganisms. This review synthesizes evidence for three prerequisites—sunlight, photosensitizers, and suitable microorganisms—and evaluates the likelihood that photoelectrotrophy occurs in natural environments based on insights from model systems. Proposed mechanisms of photoelectron uptake and transfer, including mediator-assisted and direct interfacial pathways, are then summarized and linked to major biogeochemical cycles of carbon, nitrogen, and other elements. Finally, environmental implications such as redox cycling and reactive oxygen species production are discussed, and opportunities and challenges for harnessing photoelectrotrophy in energy and environmental applications are outlined.