A novel char-forming agent named PEIC was designed and synthesized combining pentaerythritol octahydrogen tetraphosphate (PEPA) and tris(2-hydroxyethyl) isocyanurate. PEIC was combined with the silica-gel-microencapsulated ammonium polyphosphate (OS-MCAPP), preparing intumescent flame-retardant polypropylene (PP) composites. The results of the limiting oxygen index (LOI) show that the composite containing 30 wt % IFR with OS-MCAPP:PEIC = 2:1 presents the optimal LOI of 32.7%. Meanwhile, the cone calorimeter tests show that its peak heat release rate is 432 kW m −2 , which decreases by 62.1% compared with that of pure PP, showing a high-efficient flame retardancy. The exhibited UL-94 V-0 rating for all the composites indicates that the IFR composed of PEIC and OS-MCAPP has high-efficient flame retardancy in PP. The analysis of residue char reveals that PEIC could improve the quality of char in compactness, intumescentia, and the degree of graphitization. Further, the effect of IFR on the mechanical properties of PP composites was also evaluated and discussed.