The invention discloses a method for degrading polybrominated diphenyl ether by combining surfactant solubilization and UV technology, which belongs to the technical field of environment-friendly halogenated aryl hydrocarbon organic pollutant treatment. The method adopts the technical proposal that surfactant solubilization of 2,2',4,4',5-pentabromated diphenyl ether is improved in a hydrophobic environment provided by nonionic surfactant micelle (Brij 35 or Brij 38) under the conditions of normal temperature and pressure, water bath and ultrasonic sound; and the 2,2',4,4',5-pentabromated diphenyl ether which is dissolved in a surfactant solution is subjected to UV advanced treatment at normal temperature and pressure and then subjected to stepwise debromination reaction or intermolecular elimination and annulation reaction to generate intermediate products, namely PBDEs from monobromo to tetrabromo and polybrominated dibenzofuran (PBDFs) from monobromo to tetrabromo. The whole technology has short time consumption and high efficiency, and the method can selectively degrade target pollutant without damaging a surfactant, provides convenience for recycling of the surfactant, and has good application prospect in the aspect of remediation of soil polluted by the PBDEs in electronic waste recycling sites.