In this study, cobalt ferrite (CoFe2O4) nanoparticles were synthesized by two novel methods. The first method is based on the thermolysis of metal-NN complexes. In the second method, a template free sonochemical treatment of mixed cobalt and iron chelates of α-nitroso-β-naphthol (NN) was applied. Products prepared through method 1 were spherical, with high specific surface area (54.39 m2 g−1) and small average crystalline size of 13 nm. However, CoFe2O4 nanoparticles prepared by method 2 were in random shapes, a broad range of crystalline sizes and a low specific surface area of 25.46 m2 g−1 though highly pure. A Taguchi experimental design was implemented in method 1 to determine and obtain the optimum catalyst. The structural and morphological properties of products were investigated by x-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, Brunauer–Emmett–Teller and dynamic laser light scattering. The crystalline size calculations were performed using Williamson–Hall method on XRD spectrum. The photocatalytic activity of the optimum nanocrystalline cobalt ferrite was investigated for degradation of a representative pollutant, methylene blue (MB), and visible light as energy source. The results showed that some 92% degradation of MB could be achieved for 7 h of visible light irradiation.