Bis(2-propyloxy)calix[4]crown-6 (BPC6) is an effective separation agent for cesium removing from spent nuclear fuel. The study on radiolytic behavior of BPC6 itself under γ-irradiation was required for evaluating its feasibility of practical application. It was found that BPC6 exhibited excellent radiation stability at dose less than 100 kGy. However, the isopropyl groups in BPC6 under- went oxidation and dealkylation to form carbonyl groups and phenolic hydroxyl groups at dose above 300 kGy, respectively. When the dose was more than 1000 kGy, the ring opening of crown ether structure of BPC6 resulted in the formation of phenolic hydroxyl groups as well. The formation of radiolytic products containing phenolic hydroxyl groups during the irradiation of BPC was confirmed by using FeCl 3 as a probe. Combining with the radiolytic behavior of two model chemicals (1-isopropoxybenzene and benzo-18-crown-6 ether), the radiolytic behavior and mechanism of BPC6 under -irradiation was testified further. The study on radiolytic behavior of BPC6 itself under γ-irradiation was required for evaluating its feasibility of practical application. Bis (2-propyloxy) calix [4] crown-6 (BPC6) is an effective separation agent for cesium removal from spent nuclear fuel. . It was found that BPC6 showed excellent radiation stability at doses less than 100 kGy. However, the isopropyl groups in BPC6 under-went oxidation and dealkylation to form carbonyl groups and phenolic hydroxyl groups at doses above 300 kGy, respectively. When the dose was more than 1000 kGy, the ring opening of crown ether structure of BPC6 resulted in the formation of phenolic hydroxyl groups as well. The formation of radiolytic products containing phenolic hydroxyl groups during the irradiation of BPC was confirmed by using FeCl 3 as a probe. with the radiolytic behavior of two model chemicals (1-isopropoxybenzene and benzo-18-crown-6 ether), the radiolytic behavior and mechanism of BPC6 under-irradiation was testified further.