Polyurea was compounded with ammonium polyphosphate and expandable graphite and the morphology was studied by atomic force microscopy. The thermal degradation of polyurea and polyurea compounded with the additives has been investigated using thermogravimetry coupled with Fourier Transform infrared spectroscopy and mass spectrometry. The study of the thermal degradation and the parameters affecting the thermal stability of PU is essential in order to effectively design flame retarded polyurea. In general, thermal decomposition of polyurea occurs in two steps assigned to the degradation of the hard segment and soft segment, respectively. Adding these additives accelerates the decomposition reaction of polyurea. However, it is clear that more char is formed. This char is thermally more stable than the carbonaceous structure obtained from neat PU. The intumescent shield traps the polymer fragments and limits the evolution of small flammable molecules that are able to feed the flame.