A commercial cyclic diphosphonate ester (TPMP) and melamine (MA) was combined and added to polyamide 6 (PA6) to prepare the fire retardant PA6. An increase of the oxygen index to 28.6 as well as an improvement of the UL-94 classification to V-0 rating was observed. Cone measurements explained the rate of heat release (RHR) decreased and TGA showed the early decomposition and high solid residue due to co-addition of TPMP and MA, suggesting the occurrence of synergistic effect of TPMP and MA on fire resistance of PA6. The morphology of the char developed during combust ion showed the appearance of thick, intumescent cells on the surface of retardant PA6, which protects the underlying material from the action of the heat flux or flame and limits the diffusion of combustible volatile products towards the flame and oxygen.