CeFeO3 nanoparticles have been synthesized by using a fast microwave-thermal treatment method in the presence of PVP at temperatures ranging from 500 to 700 °C. The nanopowders synthesized have been characterized by field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and vibrating-sample magnetometer (VSM). Nanopowders synthesized present different crystallite sizes, ranging from 30 to 60 nm, and a weak ferromagnetic behavior which increase with the calcination temperature. The optical band gap of the CeFeO3 nanopowders was obtained by UV–Vis spectroscopy (UV-Vis) measurements and resulted to decrease with the calcination temperature. The photocatalytic activity of CeFeO3 nanopowders was tested in the degradation of methylene blue (MB) under visible light (400 nm < λ < 700 nm). The higher photoactivity toward MB degradation under visible light of CeFeO3 sample obtained at the lower calcination temperature was attributed to its smaller particle size. Subsequently, CeFeO3/GO nanocomposite was prepared and investigated. The observed photocatalytic efficiency of the synthesized CeFeO3/GO was 97% after 25 min which showed excellent photocatalytic activity. The combination of CeFeO3 nanoparticles with graphene oxide could be a way to develop a novel potential photocatalyst toward highly efficient degradation of organic dyes under visible light radiation.