To enhance the flame‐retardant characteristics of ceramifiable polyethylene (PE) composites, a composite flame retardant comprising ammonium polyphosphate (APP) and melamine cyanurate (MCA) was integrated. This addition markedly bolstered their flame‐retardant attributes. A meticulous exploration was conducted to ascertain the impacts of APP and MCA on the ceramifiable PE composites' visible morphology, mechanical robustness, and dimensional constancy, and to study the phase transition and microstructure deformation during sintering. Findings underscored that the amalgamation of APP/MCA markedly enhanced the flame resistance of these ceramifiable composites, registering a limiting oxygen index of 25.6% and achieving the vertical burning test (UL‐94) rating of V‐0. The collaborative flame‐retardant action of APP/MCA significantly enhanced the flame resistance of the PE composites while effectively mitigating the composite's propensity to drip. Upon detailed phase analysis, a eutectic reaction was observed between APP and wollastonite fiber, culminating in the genesis of a novel crystalline phase, calcium pyrophosphate (Ca2P2O7). When subjected to elevated temperatures, glass–ceramics manifest with both crystalline and vitreous phases. The proportion of the vitreous phase plays a pivotal role in influencing the ceramic's overall performance.