The chemical blowing agent plays a crucial role in enhancing the performance of the polyethylene (PE) foaming resin during the rotational foaming process. Previously, the conventional blowing agent of the PE resin commonly used pure azodicarbonamide (AZ). It had the unavoidable drawbacks of releasing NH 3 and exhibiting strong reactions during the rotational foaming process. Meantime, pure AZ had a relatively high decomposition temperature, resulting in a sharp foaming process. To address the above issues, this work developed a uniquely designed blowing agent system. In this study, a novel blowing agent for the PE resin was successfully synthesized by a one-pot method. This blowing agent consisted of an activator and AZ, which exhibited a lower decomposition temperature and a milder decomposition rate than AZ. The activator was constituted of small-sized ammonium dihydrogen phosphate on the AZ surface, which could be decomposed properly and deliver phosphoric acid and H 2 O during the foaming process. Then, AZ reacted with H 2 O under phosphoric acid catalysis. Also, this reaction generated CO 2 emission while reducing the emission of NH 3 through recombination with phosphoric acid. Moreover, phosphoric acid catalysis caused a decrease in the AZ decomposition temperature. Meantime, the thermal coupling appeared during the foaming process, which could further reduce the decomposition rate. Consequently, the small activator played a key role in regulating cell formation and diffusion. Compared to AZ, the novel blowing agent system significantly reduced the cell diameter of the PE foam resin and enhanced its flexural modulus by 50%. Furthermore, the novel blowing agent facilitated better demolding performance and improved the surface morphology of the PE foam product. This research provides significant foaming behavior regulation for the PE resin during industrial applications.