A series of InVO4 incorporated with multi-wall carbon nanotubes (CNTs) composite nanofibers were successfully synthesized by an electrospinning technique. The as-collected nanofibers were calcined at 550 °C in air to remove polyvinyl pyrrolidone (PVP), which could enable InVO4 to crystallize. InVO4 in the composite illustrated a hollow fibrous morphology and orthorhombic phase, and CNTs were embedded or coated on the InVO4 hollow nanofibers. High-resolution transmission emission microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR) spectra and X-ray photoelectron spectroscopy (XPS) spectra illustrated that CNTs were existed in the composites. The optical properties measured using UV–Vis diffuse reflectance spectroscopy (DRS) confirmed that the absorbance of InVO4 nanofibers increased in the visible light region with the incorporation of CNTs. The photocatalytic performance of the samples was investigated by the degradation rhodamine B (Rh B) under visible light irradiation. The CNTs/InVO4 nanofibers in Rh B degradation displayed a higher photocatalytic activity than pure InVO4 nanofibers and 10%CNTs/InVO4 nanoparticles. The degradation showed an optimized photocatalytic oxidation for InVO4 nanofibers incorporated with 10wt% CNTs. The enhanced photocatalytic activity might be ascribed to the role of CNTs as an electron transporter and acceptor in the composites, which could effectively inhibit the charge recombination and facilitate the charge transfer.