A novel flame retardant heax-[N,N',N ''-tris-(2-amino-ethyl)-[1,3,5] triazine-2,4,6-triamine] cyclotriphosphazene (HTTCP) containing phosphazene and triazine groups was synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), solid-state H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy. HTTCP was applied to PLA matrix. The results of thermal gravimetric analysis (TGA), the limited oxygen index (LOI), and cone calorimeter test indicated that the HTTCP enhanced the thermal stability and flame retardant properties of PLA. When the mass fraction of HTTCP was 25 wt %, the PLA composite acquired a LOI value of 25.2% and the lower pk-HRR at 290 kW/m(2). The excellent flame retardancy of HTTCP was attributed to the group synergistic effect between phosphazene and triazine groups. However, when combined HTTCP with APP (the total amount remaining 25 wt %, the ratio of HTTP to APP are 1:1 and 1:2), high values of LOI (over 40%) and UL94 V-0 rating without dripping reached simultaneously. Meanwhile, the heat release rate, total heat release and mass loss rate were all decreased dramatically. Scanning electron microscopy (SEM) demonstrated that HTTCP/APP system benefited to the formation of more intumescent, dense, compact char layer on the materials surface which could effectively prevent the underlying material from degradation during burning. (C) 2016 Wiley Periodicals, Inc.