Benzalkonium chlorides (BACs), as typical cationic surfactants and biocides widely applied in household and industrial products, have been frequently detected as micropollutants in many aquatic environments. In this study, the combination of UV irradiation and chlorine (UV/chlorine), a newly interested advanced oxidation process, was used to degrade dodecylbenzyldimethylammonium chloride (DDBAC). UV/chlorine showed synergistic effects on DDBAC degradation comparing to UV irradiation or chlorination alone. Radical quenching experiments indicated that degradation of DDBAC by UV/chlorine involved both UV photolysis and radical species oxidation, which accounted for 48.4% and 51.6%, respectively. Chlorine dosage and pH are essential parameters affecting the treatment efficiency of UV/chlorine. The pseudo first order rate constant (kobs, DDBAC) increased from 0.046 min−1 to 0.123 min−1 in response to chlorine dosage at 0–150 mg/L, and the degradation percentage of DDBAC within 12 min decreased from 81.4% to 56.6% at pH 3.6–9.5. Five main intermediates were identified and semi-quantified using HPLC-MS/MS and a possible degradation pathway was proposed. The degradation mechanisms of DDBAC by UV/chlorine included cleavage of the benzyl-nitrogen bond and hydrogen abstraction of the alkyl chain. Trichloromethane (TCM), chloral hydrate (CH), trichloropropanone (TCP), dichloropropanone (DCP) and dichloroacetonitrile (DCAN) were detected using GC-ECD. The formation of chlorinated products increased rapidly initially, then decreased (TCM, TCP, DCP and DCAN) or remained stable (CH) with extended treatment. The actual formation of TCM peaked at 30 min (50.3 μg/L), while other chlorinated products did not exceed 10 μg/L throughout the process. Based on the luminescent bacterial assay, DDBAC solution underwent almost complete detoxification subjected to UV/chlorine treatment for 120 min, which is more effective than UV irradiation or chlorination alone. •UV/chlorine showed synergistic degradation of DDBAC than UV and chlorination.•DDBAC degraded through both UV photolysis and radicals oxidation during UV/chlorine.•Degradation pathway of DDBAC during UV/chlorine oxidation was proposed.•Formation of chlorinated products decreased with extended UV/chlorine oxidation.•UV/chlorine oxidation was efficient at DDBAC detoxification.