Nanostructured Co1-xZnxFe2O4 (0≤x≤0.5) catalyst synthesized by the microwave combustion method was employed for the photocatalytic degradation of rhodamine B (RhB) under visible light. Doping of Zn2+ ions in the cobalt ferrite matrices were confirmed by the diffraction peak-shift towards lower angles. The Williamson-Hall method was used to calculate the crystallite size considering the strain components. The conduction band (CB) and valence band (VB) edges of all the samples were calculated using optical studies. Photoluminescence analysis performed at an excitation wavelength of 330 nm disclosed the rate of recombination of electron-hole pairs and the defects present. Photocatalytic degradation of RhB with pure cobalt ferrite system was performed at pH 2.0 by varying the time, initial concentration and addition of hydrogen peroxide to behave like a Fenton like process. However the effective photodegradation of all zinc doped cobalt ferrite were done at optimal RhB concentration of 6 mg/l at identical operational conditions. Among all the samples Co0.6Zn0.4Fe2O4 exhibited an enhanced degradation efficiency of 99.9% at visible light exposure time of 210 min. The degradation pathway followed first order rate rather than the second order rate kinetics. Based on the values of CB and VB edges in the Co0.6Zn0.4Fe2O4 system, possible routes for the degradation of RhB are suggested. © 2016 Elsevier Ltd and Techna Group S.r.l.