Hydrogen energy is considered a competitive and environmentally friendly carrier owing to its high calorific value, abundant reserves, carbon-free emission, and renewability. Water splitting for sustainable production of hydrogen from water via sunlight or clean energy derived electricity has attracted paramount attention. Photocatalytic water splitting provides a clean solution to produce hydrogen by taking advantage of abundant solar power. Due to their unique physico-chemical properties, metal/metal oxide based composite electrospun semiconductor photocatalysts show great potential to supplant some of the non-oxide photocatalysts and other nanostructures in water splitting. The key issues to the commercialization and scale-up production remain on the fabrication, modification and performance of photocatalysts. In this review article, we showcase recent significant progress in the fabrication of semiconductor photocatalysts toward water splitting based on versatile electrospinning. The modification and performance improving strategies for a wide range of metal/metal oxide (single, mixed, metal/carbon cocatalysts) electrospun semiconductors including the structure and compositional engineering are presented. Furthermore, we also discuss the challenges and future perspectives of electrospinning toward the rational design and facile fabrication of photocatalysts.