CeO₂/ZnO-based photocatalytic materials were synthesized by the sol-gel method in order to establish heterojunctions that increase the degradation efficiency of some types of antibiotics by preventing the recombination of electron–hole pairs. The synthesized materials were analysed by XRD, SEM, EDAX, FTIR, and UV-Vis. After several tests, the optimal concentration of the catalyst was determined to be 0.05 g‧L⁻¹ and 0.025 g‧L⁻¹ for chlortetracycline and 0.05 g‧L⁻¹ for ceftriaxone. CeO₂/ZnO assemblies showed much better degradation efficiency compared to ZnO or CeO₂ tested individually. Sample S3 shows good photocatalytic properties for the elimination of ceftriaxone and tetracycline both from single solutions and from the binary solution. This work provides a different perspective to identify other powerful and inexpensive photocatalysts for wastewater treatment.