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[Display omitted] • S-nZVI/PAA system could effectively degrade CIP in 60 min. • S doping promotes Fe(II)/Fe(III) cycling and improves the degradation efficiency of CIP. • Reactive oxygen species (ROS) and Fe(IV) contributed to CIP elimination. • S-nZVI/PAA system was effective at mitigating the toxicity of CIP. As commonly observed water pollutants, antibiotics can induce antibiotic-resistance genes and pose significant risks to ecosystems and human health. Consequently, eliminating antibiotics from water environments is essential. We used the sulfidated nano zero-valent iron (S-nZVI) to activate peracetic acid (PAA) system to facilitate ciprofloxacin (CIP) degradation. S-nZVI was fabricated using the liquid-phase method, yielding particles with a predominantly spherical morphology and an average size range of 70–110 nm. Under optimized conditions, the S-nZVI/PAA system had a remarkable CIP removal efficiency of 95.61 % in 60 min. The reactive oxygen species (ROS) and Fe species (Fe(IV)) generated in the S-nZVI/PAA system were fundamental in facilitating the degradation of CIP. The reaction products of CIP were identified, and the toxicity was reduced after degradation. Additionally, an investigation was conducted to explore the practical application potential of the S-nZVI/PAA system. The work provides a promising strategy for the removal of antibiotics in water, and gives new insights into the mechanism of S-nZVI activating PAA to remove antibiotics. [ABSTRACT FROM AUTHOR]