Fe3+ doped TiO2 composite nanofiber membranes and pure TiO2 nanofiber membranes were prepared through electrospinning, and were applied to the photocatalytic degradation of malachite green (MG) in aqueous solutions under simulated sunlight. The effects of ferric ion content, initial concentration of MG, photocatalyst loading, and recycling behavior were studied. Microscopic characterization showed that the products have fiber morphology with bent property and favorable continuity. The degradation results showed that TiO2 nanofiber membranes containing 0.8 mol% Fe3+ performed the best photocatalytic activity against MG under identical light irradiation. The TiO2:Fe3+ composite nanofiber membranes maintained their photocatalytic efficiency through seven recycling processes.