In the present work, a heterojunction nanofiber material α-Fe2O3/NiTiO3, was synthesized by a two-step method involving calcining process. The characteristic nature of the materials such as composition and optical properties were examined by X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) and the results confirmed the high crystalline behavior and fiber-like heterostructures of the α-Fe2O3/NiTiO3 composites. The α-Fe2O3/NiTiO3 heterojunction nanofibers were observed to exhibit an enhanced performance in the photocatalytic degradation of organic dye Rhodamine B (RhB) under the visible light irradiation. The superior absorptive behavior of α-Fe2O3/NiTiO3 heterojunction nanofibers to pure α-Fe2O3 nanofibers in the longer wavelength region was confirmed by UV–vis Diffuse Reflectance Spectral (DRS) studies. The photoluminescence (PL) spectral studies indicated that the recombination of photogenerated electron–hole pairs has been decreased in the case of α-Fe2O3/NiTiO3.