The triazine hindered amine (THA) nitroxide radicals are important to the preparation of halogen-free flame retardants, but the traditional methods using peracetic acid was limited in further sustainable development in industry. In this work, the bicarbonate-activated hydrogen peroxide system with ethyl acetate as the solvent (BAP-EA system) was firstly employed in TH-7 nitroxide radicalization, which exhibited excellent performance with 99% yield of TH-7-(NOÁ) 2 at 30 C. To further explore the mechanism, the bicarbonate transformation, the generation of reactive oxygen species (ROS), and the effect of ROS were explored by LC-MS, 13 C-NMR, EPR, et al. The results indicated that HCO 4À was generated in BAP system, and then further produced ROS ( 1 O 2 , ÁO 2 À and ÁOH) to participate in the radicalization. ROS also exhibits synergistic effects in BAP-EA system, and further enhanced the reactivity of ROS in TH-7 nitroxide radicalization. Moreover, in the flame retardancy test, NOR 116 synthesized in BAP-EA system displayed excellent flame retardant synergy with aluminum hypophosphite (AH) in polypropylene (PP). This work provides a novel insight in green process of THA nitroxide radicalization for halogen-free flame retardants.