TiO2/LaFeO3 heterostructures were fabricated by electrospinning technique and hydrothermal synthesis method. The physicochemical properties of the catalysts were characterized by scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FUR) and ultraviolet-visible diffuse reflectance spectra (UV-Vis). The photocatalytic activity of TiO2/LaFeO3 micro-nanofibers toward the decomposition of methylene blue(MB) was investigated. The results indicate that defect sites of incompletely carbonized TiO2 fibers are favorable for the growth of LaFeO3 nanoparticles. The band gap of TiO2/LaFeO3 heterostructures is lower than TiO2 improving the photocatalytic activity. After 140 min TiO2/LaFeO3 heterostructures exhibited 65. 34% for MB under UV light, and the photocatalytic mechanism of TiO2/LaFeO3 heterostructures were analyzed and discussed.