An organic triazine charring agent hybrid with zinc oxide (OTCA@ZnO) was prepared and well characterized through Fourier transform infrared spectrometry (FTIR), solid-state nuclear magnetic resonance (SSNMR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The flame retardancy and thermal behaviour of intumescent flame retardant ethylene-vinyl acetate (EVA) composites combining OTCA@ZnO and ammonium polyphosphate (APP) were investigated using limited oxygen index (LOI), UL-94 vertical burning, cone calorimetry and TGA. The structure and morphology of chars were investigated by scanning electron microscopy (SEM), FTIR, laser Raman spectroscopy analysis (LRS) and X-ray photoelectron spectroscopy (XPS). Results revealed that OTCA@ZnO exhibited excellent thermal stability and dispersity after hybridization. The flame retardancy and smoke suppression properties of EVA were significantly improved by introducing APP/OTCA@ZnO. TGA results indicated that APP/OTCA@ZnO presented an excellent synergistic effect and promoted the char formation of EVA composites. Residue analysis results showed more char with high quality connected by richer P-O-C, P-N and P-O-Si structures was formed in APP/OTCA@ZnO system than APP/HOTCA/ZnO system, which consequently suppressed more efficiently the combustion and smoke production due to the in situ catalytic carbonization effect of hybrid.