Herein, we report a theoretical and experimental study on the photocatalytic activity of CeO 2 ZnS, and ZnS decorated CeO 2 nanoparticles prepared by a microwave-assisted solvothermal method. Theoretical models were established to analyze electron transitions primarily at the interface between CeO 2 and ZnS. As observed, the particle morphology strongly influenced the photocatalytic degradation of organic dye Rhodamine B. A model was proposed to rationalize the photocatalytic behavior of the prepared decorated systems taking into account different extrinsic and intrinsic defect distributions, including order-disorder effects at interfacial and intra-facial regions, and vacancy concentration. V C 2014 AIP Publishing LLC.