A facile two-step synthesis route combining electrospinning and hydrothermal techniques has been performed to obtain Bi2Ti2O7/TiO2 heterostructured submicron fibers. Bi2Ti2O7 nanosheets were grown on the surface of TiO2 submicron fibers. The density of the nanosheets increased with higher precursor concentration of the Bi/Ti reaction raw materials. UV-visible (UV-vis) diffuse reflectance spectroscopy indicated that the absorption spectrum of the Bi2Ti2O7/TiO2 composite extended into the visible-light region. Photocatalytic tests showed that the Bi2Ti2O7/TiO2 heterostructures possess a much higher degradation rate of rhodamine B than the unmodified TiO2 submicron fibers under visible light. The enhanced photocatalytic activity can be attributed to the synergistic effect between improved visible-light absorption and the internal electric field created by the heterojunctions. The effective separation of photogenerated carriers driven by the photoinduced potential was demonstrated by the photoelectrochemical analysis.Electronic supplementary materialThe online version of this article (doi:10.1186/s11671-016-1408-7) contains supplementary material, which is available to authorized users.