Two-dimensional (2D) MoS2 nanosheets vertically supported on TiO2/PVDF flexible fibers have been successfully synthesized by combining electrospinning with a low temperature hydrothermal method without acid. The morphology of the 2D MoS2 nanosheets could be controlled by adjusting the experimental parameters. The loaded 2D MoS2 nanosheets can not only broaden the light capture range of TiO2, but also greatly inhibit the recombination rate of photogenerated electron-hole pairs. Due to the synergistic effect between MoS2 and TiO2, the photocatalytic rate for levofloxacin hydrochloride is about 40 times higher than that for MoS2 only. Recycle experiments have proved the stability and reusability of TiO2/PVDF@2D MoS2 nanosheets. The mechanism is investigated by quenching experiments. The results show that the superoxide anion radical (•O2 -), the hydroxyl radical (•OH) and the hole (h+) all have contributions to photocatalysis. This work widens the range of materials to synthesize the composites of 2D MoS2 nanosheets and provides a new and gentle method for preparing flexible large-scale heterostructures for environmental protection.