Environmental-friendly photocatalytic technology is attracting considerable attentions in the filed of antibiotic degradation. In this work, an innovative Ag/ZnO/Bi2WO6 catalyst was fabricated using sol–gel and ultrasonic methods for the degradation cefuroxime sodium in wastewater. The optimized Ag/ZnO/Bi2WO6 photocatalyst demonstrated the a remarkable 77.0% photocatalytic efficiency within 180 min under simulated solar sunlight, with an apparent rate constant of 0.01085 min− 1. This efficiency is notably 6.02 and 1.41 times higher than that of pure ZnO and Ag/ZnO, respectively. The Ag/ZnO/Bi2WO6 photocatalyst achieved a degradation efficiency of up to 72.3% in tap water and polluted river water, while achieving 65.7% degradation in pulping wastewater and pharmaceutical wastewater. Experiments involving reactive species scavenging and electron paramagnetic resonance implied that hydroxide radicals were the predominant active species responsible for the degradation. The enhanced catalytic mechanism and degradation pathway were elucidated, providing valuable insights into the construction and development of high-performance catalysts based on zinc oxide.