This paper studied the photocatalytic degradation of methylene blue (MB) using polymeric membrane impregnated with ZnO nanostructures under UV-light and sunlight irradiation. ZnO nanoparticles and ZnO nanowires were prepared using the hydrothermal technique. Cellulose acetate polymeric membranes were fabricated by the phase inversion method using dimethylformamide (DMF) as a solvent and ZnO nanostructures. The structural properties of the nanostructures and the membranes were investigated using XRD, SEM, FTIR, and TGA measurements. The membranes were tested for photocatalytic degradation of MB using a UV lamp and a sunlight simulator. The photocatalytic results under sunlight irradiation in the presence of cellulose acetate impregnated with ZnO nanoparticles (CA-ZnO-NP) showed a more rapid degradation of MB (about 75%) compared to the results obtained under UV-light irradiation degradation (about 30%). The results show that CA-ZnO-NP possesses the photocatalytic ability to degrade MB efficiently at different levels under UV-light and sunlight irradiation. Modified membranes with ZnO nanoparticles and ZnO nanowires were found to be chemically stable, recyclable, and reproducible. The addition of ZnO nanostructure to the cellulose membranes generally enhanced their photocatalytic activity toward MB, making these potential membranes candidates for removing organic pollutants from aqueous solutions.