Solar-driven semiconductor photocatalysts for solving global energy shortage and environmental pollution have attracted massive attention. Multi-structure hollow nanofibers (MSHFs) photocatalyst offers many advantages, including abundant surface area for multiple light harvesting and interface redox reaction, heterostructured thin shell for expediting charge separation and transportation and large length-diameter ratio for easily recycling. Herein, we summarize the latest development of MSHFs materials in terms of controlled synthesis approaches and applications in photocatalysis. The synthetic strategies are mainly classified into two categories, containing templating method and electrospinning approach. These MSHFs have wide applications in H-2 production, CO2 reduction, organic compound degradation and dye-sensitized solar cells (DSSCs). To the end of the review, perspectives on the future research and development of MSHFs are also discussed.