Thermal protection of chemical storage tanks is very important when a fire accident occurs. Intumescent coating on the surface of the tank is one of efficient measures to prevent fire. It is essential to investigate the interaction between heat transfer and burning behavior of intumescent coating, which will affect the fire-proof performance of the coating. In this paper, ADP/MPP epoxy intumescent coatings were prepared by adding the intumescent flame retardants aluminum diethylphosphinate (ADP) and melamine phenyl phosphonate (MPP) into epoxy resin (EP). The heat transfer process and burning behavior were analyzed by temperature distribution, thermogravimetric analysis (TGA), cone calorimeter and scanning electron microscopy (SEM). The results showed that the ratio of ADP and MPP, the intumescent characteristics and the structure of the char layer can affect the heat transfer of the coating remarkably. The residual char morphology analysis shows that the coating containing ADP and MPP is more capable of forming a well-structured char layer structure and shows a good thermal insulation performance. •The relationship between heat transfer process and burning behavior were investigated.•SEM images were processed and statistically analyzed the porosity and bubble pore area of the char layer.•The epoxy intumescent coating containing ADP and MPP had better flame retardancy and thermal insulation properties.