In this work, we studied the mechanism of the fire retardancy of ammonium polyphosphate (APP) in polyurethane (PU). Indeed, according to the limiting oxygen index test, the efficiency of APP in PU coating was proven. On the one hand, thermogravimetric analyses showed that the addition of APP to PU accelerates the decomposition of the matrix but leads to an increase in the amount of high-temperature residue, under an oxidative or inert atmosphere. This stabilized residue acts as a protective thermal barrier during the intumescence-fire retardancy process. On the other hand, spectroscopic analysis of the charring materials using infrared spectroscopy, MAS NMR of the solid state, and ESR enables better understanding of the carbonization process and, consequently, of the intumescence phenomenon. It has been shown that the char resulting from PU consists of an aromatic carbonaceous structure which condenses and oxidizes at high temperature. In the presence of APP, a reaction between the additive and the polymer occurs, which leads to the formation of a phosphocarbonaceous polyaromatic structure. Moreover, this char is strongly paramagnetic. The presence of large radical species, such as a polyaromatic macromolecule trapping free radicals, was demonstrated. Both of these characteristics help to explain the fire-retardant performance of PU/APP.