Modified ammonium polyphosphate (MAPP) as a novel mono-component intumescent flame retardant (IFR) was prepared via the ionic exchange between ammonium polyphosphate (APP) and piperazine sulfonate, which is synthesized by self-assembly using 1-(2-Amioethyl) piperazine (AEP) and p-amino benzene sulfonic acid (ASC) as raw materials. This all-in-one IFR integrating three functional elements (carbon, acid, and gas source) showed more efficient flame retardancy and excellent smoke suppression as well as better mechanical properties than the conventional APP. The incorporation of 22.5 wt.% MAPP into polypropylene (PP) eliminated the melt dripping phenomenon and passed the UL-94 V-0 rating. The results of the cone calorimetry test (CCT) revealed that the release of heat, smoke, and CO is significantly decreased, demonstrating that this novel IFR endows PP with excellent fire safety more effectively. For PP/MAPP composites, a possible IFR mechanism was proposed based on the analysis of the pyrolysis gas and char residues.