AbstractA new intumescent flame retardant (IFR) system consisting of ammonium polyphosphate (APP) and charing‐foaming agent (CFA) and a little organic montmorillonite (OMMT) was used in low‐density polyethylene (LLDPE)/ethylene‐vinyl acetate (EVA) composite. According to limiting oxygen index (LOI) value and UL‐94 rating obtained from this work, the reasonable mass ratio of APP to CFA was 3 : 1, and OMMT could obviously enhance the flame retardancy of the composites. Cone calorimeter (CONE) and thermogravimetric analysis (TGA) were applied to evaluate the burning behavior and thermal stability of IFR‐LLDPE/EVA (LLDPE/EVA) composites. The results of cone calorimeter showed that heat release rate peak (HRR‐peak) and smoke production rate peak (SPR‐peak) and time to ignition (TTI) of IFR‐LLDPE/EVA composites decreased clearly compared with the pure blend. TGA data showed that IFR could enhance the thermal stability of the composites at high temperature and effectively increase the char residue. The morphological structures of the composites observed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) demonstrated that OMMT could well disperse in the composites without exfoliation, and obviously improve the compatibility of components of IFR in LLDPE/EVA blend. The morphological structures of char layer obtained from Cone indicated that OMMT make the char layer structure be more homogenous and more stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009