Flexible TiO2 nanofibres were fabricated by electrospinning with Ti(SO4)2, polyvinyl pyrrolidone (PVP), dimethyl formamide(DMF) and deionized water as starting materials. The samples were characterized with XRD, FESEM, TEM and TG-DTA. The results reveal that the obtained TiO2 nanofibres are flexible and polycrystalline structure. The mean diameter of the TiO2 nanofibres is about 100 nm, and the length is greater than 300 μm. The influence of calcination temperatures on the photocatalytic effect for TiO2 nanofibres was investigated through methyl orange, rhodamine-B and phenol as degradation compounds. The photocatalytic experiments results indicate that flexible TiO2 nanofibres possess high degradation rates for these three degradation compounds. The formation mechanism of the flexible TiO2 nanofibres was also discussed