Iron-based PAA activation process is a promising advanced oxidation process for water decontamination which depends on Fe(II) as the main reactive site for PAA activation, resulting in various reactive oxidative species (ROSs) generation. For practical application, the impact of water matrix chloride ion (Cl-) on ROSs production and contaminants removal should be carefully considered. In this study, it's found that the introduction of Cl- (0.1-10 mM) could significantly enhance the reaction rate of the rapid stage (kobs1) up to 2.15 times at the initial pH of 4.25 in the Fe(II)/PAA system. Further studies demonstrated that the improved removal capacity of NAP resulted from Cl- induced R-O• generation as indicated by the exposure dose of R-O• increasing from 7.74 × 10-11 M•s to 1.44 × 10-10 M•s, rather than chlorine-containing radicals' generation. DFT calculation results suggested that the formed Fe(II)-Cl- complexes could easily activate PAA to generate more ROSs for NAP removal. Moreover, Fe(II)/PAA treatment can alleviate the biological toxicity of pollutants via both the Escherichia coli test and toxicity assessment. The obtained new knowledge manifested that Cl- can boost ROSs generation and conversion in iron-based PAA systems, providing guidance for the efficient decontamination of chlorine-containing sewage with PAA-based AOPs.