-divinyl-3-aminopropyltriethoxysilane, and the modified lignin (CLig) was combined with ammonium polyphosphate (APP) as intumescent flame retardant to be applied in poly(Lactic acid) (PLA). The flame retardancy, combustion behavior and thermal stability of PLA composites were studied by the limited oxygen index (LOI), vertical burning testing (UL-94), cone calorimetry testing (CCT) and thermogravimetric analysis (TGA), respectively. The results showed a significant synergistic effect between CLig and APP in flame retarded PLA (PLA/APP/CLig) occured, and the PLA/APP/CLig had better flame retardancy. CCT data analysis revealed that CLig and APP largely reduced the peak heat release rate (PHRR) and total heat release rate (THR) of PLA, indicating their effectiveness in decreasing the combustion of PLA. TGA results exhibited that APP and CLig improved the thermal stability of PLA at high temperature. The analysis of morphology and structure of residual char indicated that a continuous, compact and intumescent char layer on the material surface formed during firing, and had higher graphitization degree. Mechanical properties data showed that PLA/APP/CLig had higher tensile strength as well as elongation at break.