Co1-xMgxFe2O4 (0≤x≤0.5) spinel nanoparticles were synthesized by a simple microwave combustion method. The characterization of the samples were performed using X-ray diffraction (XRD) analysis, scanning electron (SEM) microscopy, energy dispersive X-ray (EDX) analysis, UV–visible and diffuse reflectance (DRS) spectroscopy, photoluminescence (PL) spectroscopy, Fourier transformed infrared (FT-IR) spectroscopy and vibrating sample magnetometry (VSM) analysis. The XRD patterns indicate the formation of cubic inverse spinel structure. The calculated average crystallite size using Debye Scherrer's equation is found to be around 46–38 nm. The morphology of spinel nanoparticles was observed from SEM images and the elemental mapping of magnesium doped cobalt ferrite was obtained by using energy dispersive X-ray technique. Optical studies were carried out for the deeper understanding of the conduction band (CB) and valence band (VB) edges of the synthesized nanoparticles. The intrinsic stretching vibrations of Fe3+-O2- in tetrahedral sites leads to the appearance of IR band at around 573 cm−1. The magnetic properties such as remanence magnetization (Mr), coercivity (Hc) and saturation magnetization (Ms) were calculated from the hysteresis curves. The maximum photocatalytic degradation efficiency for Co0.6Mg0.4Fe2O4 is around (99.5%) when compared to that of CoFe2O4 whose efficiency is around (73.0%). The improvement in photocatalytic degradation efficiency is due to the effective separation and prevention of electron-hole pair recombination. The R2 values for the first order rate kinetics are found to be better than R2 values for the second order rate kinetics and this proves that photocatalytic degradation of RhB dye follows first order kinetics. The probable mechanism for the photocatalytic degradation of RhB dye is proposed. © 2017 Elsevier Ltd