Abstract: To develop an efficient remediation technology for naphthalene (NAP)-contaminated soil, this study systematically investigated the desorption behavior of NAP in different soil media, analyzed the effect of soil aging time, and compared the impacts of three types of desorbents— inorganic salts (calcium chloride, CaCl₂), low molecular weight organic acids (LMWOAs: citric acid (CA), oxalic acid (OA), aspartic acid (ASP)), and surfactants (Tween-80, sodium dodecyl sulfate (SDS), alkyl glycoside (APG))—on NAP desorption and their influences on the degradation of NAP by the ferrous ion (Fe(II))-activated peroxydisulfate (PDS) advanced oxidation system.The results showed that the desorption of NAP became more difficult with higher soil clay content and longer aging time. A weakly alkaline environment (pH=9.0) was favorable for NAP desorption, and the desorption process followed the pseudo-second-order kinetic model. There were significant differences in the promotion effects of the three types of desorbents on NAP desorption: LMWOAs exhibited the optimal desorption performance, among which 1.0 mmol/L CA achieved a 36.1% NAP removal rate, significantly outperforming OA and ASP. All surfactants could significantly improve desorption efficiency, with Tween-80 showing the best effect due to its low critical micelle concentration (CMC) and suitable hydrophobicity, and the promotion effect enhanced with increasing concentration. Low-concentration CaCl₂ (<10 mmol/L) promoted desorption by competing for adsorption sites, while high-concentration CaCl₂ (100 mmol/L) inhibited desorption by causing flocculation and precipitation of soil organic matter.In the subsequent oxidative degradation, surfactants and CaCl₂ inhibited NAP degradation by competing for reactive oxygen species (ROS), whereas LMWOAs exerted a positive effect. When the molar ratio of PDS/Fe(II)/CA/NAP was 15∶5∶1∶1, the NAP removal rate reached 97.5% within 120 min. This study confirmed that CA possesses the dual functions of efficiently desorbing NAP from soil and enhancing subsequent oxidative degradation, providing a theoretical basis and application potential for its use in the green and efficient remediation of organic contaminated sites.