It is difficult to enhance the char yields of polypropylene (PP) due to the preferential complete combustion. Successful formation of abundant char layer structure of PP upon flammability was obtained due to the synergistic effect of NiO, Al2O3and activated carbon (AC). From characterization of scanning electron microscopy (SEM) and transmission electron microscopy (TEM), it was revealed that the microstructure of residual char contained large amount of carbon nanotubes. Compared to the modification of AC, NiO and Al2O3alone, the combination of AC, NiO and Al2O3dramatically promotes the charring ability of PP. In the case of AC and NiO, NiO plays a role of dehydrogenation, resulting in the degradation product, while AC mainly acts as carbonization promoter. The addition of Al2O3results in higher dispersion and smaller particle size of NiO, leading to greater exposure of active sites of NiO and higher dehydrogenation and carbonization activity. Compared to the neat PP, the decomposition temperature of the PP modified by combined AC, NiO and Al2O3was increased by 90 ℃. The yield of residual char of AC-5Ni-Al-PP reached as high as 44.6%. From the cone calorimeter test, the heat release rate per unit area (HRR) and total heat release per unit area (THR) of PP composite follows the order AC-5Ni-Al-PP < AC-10Ni-Al-PP < AC-Ni-PP < AC-15Ni-Al-PP < AC-1Ni-Al-PP. Compared to the neat PP, the peak of HRR declined by 73.8%, 72.7%, 71.3%, 67.6% and 62.5%, respectively.