We report on the visible-light responsive porous assembly of Bi 2 O 3 /CeO 2 microspheres, which were synthesized via a simple hydrothermal reaction between Bi(NO 3 ) 3 ·5H 2 O and Ce(NO 3 ) 3 ·6H 2 O in the presence of ethylene glycol and ethanol. Systematic structural (X-ray diffraction (XRD)), morphological (field emission scanning electron microscopy (FE-SEM) and transmission electron microscopic (TEM)), BET surface area and diffuse reflectance spectral (DRS) analyses were carried out to characterize the formed product. The effects of experimental parameters on the microstructural and morphological behavior of Bi 2 O 3 /CeO 2 composites were discussed. The semiconductor material as obtained was evaluated as a heterogeneous photocatalyst for the photolytic degradation of an azo dye in water and the degradation was found to follow pseudo-first-order rate kinetics. The study compares the rate constants of the new hybrid catalyst to a pristine Bi 2 O 3 and CeO 2 , which has excellent catalytic properties under visible light irradiation for the degradation of Orange II dye.