Mg-Al-Fe ternary layered double hydroxides (LDH) were synthesized based on bayer red mud by calcination-rehydration method, and characterized using X-ray diffraction and thermogravimetric analysis (TGA). The synergistic flame retardant effects of ammonium polyphosphate (APP) with LDH in ethylene-vinyl acetate (EVA) composites were studied using limiting oxygen index (LOI), UL 94 test, cone calorimeter test (CCT), and smoke density test (SDT). The thermal degradation behavior of EVA/LDH/APP composites was examined by thermal gravimetric analysis-fourier transform infrared spectrometry (TG-FTIR). The results showed that LOI values decreased by incorporation of APP together with LDH; and, a suitable amount of APP in EVA/LDH composites can apparently improve UL 94 rating. The CCT results indicated that heat release rate (HRR) of the EVA/LDH/APP composites with APP decreased in comparison with that of the EVA/LDH composites. The SDT results showed that APP was helpful to suppress smoke. The TG-FTIR data showed that the composites with APP had a higher thermal stability than the EVA/LDH composites at high temperature. POLYM. ENG. SCI., 54:766-776, 2014. (c) 2013 Society of Plastics Engineers