We report a facile synthesis of p-BiOBr/n-ZnWO 4 heterostructures by hydrothermal/precipitation method as an important key player to enhance the photocatalytic degradation of Rhodamine B (RhB) dye and ciprofloxacin antibiotic. The structural and microstructural features confirm that p-BiOBr/n-ZnWO 4 heterostructures display a mixed tetragonal/monoclinic phase with the presence of several n-ZnWO 4 nanocrystals on the surface of petals of flower-like p-BiOBr microcrystals. X-ray photoluminescence (XPS) analysis of BiOBr exhibits the existence of Bi, O, and Br, whereas BiOBr/ZnWO 4-5%, in addition to Bi, O, and Br, consist of signature of Zn and W. UV–Visible spectra of p-BiOBr/n-ZnWO 4-5% showed better absorption than p-BiOBr and n-ZnWO 4, which displayed an enhanced collection of photons in the heterojunction. An intense photoluminescence emission at room temperature was observed for p-BiOBr microcrystals as compared to p-BiOBr/n-ZnWO 4. We observed the best photocatalytic activity for p-BiOBr/n-ZnWO 4-2.5% in the degradation of RhB dye at 99.4% in 25 min and CIP antibiotic at 58.2% in 170 min, which is assigned due to high surface area S BET (13 m 2/g), pore size, providing active catalytic sites for bonding chemical and surface interaction and bonding chemical between the bromide/oxides. Finally, we have investigated the use of scavengers for isopropanol, benzoquinone, and sodium azide, which proves that the hydroxyl (• OH) and superoxide (O 2′) radicals as the foremost reactive oxygen spicies (ROS) in photocatalytic degradation of RhB dye and antibiotic CIP.