Experimental and numerical studies of downward flame spread over polymethyl methacrylate (PMMA) with and without addition of triphenyl phosphate (TPP) are reported. Using the micro-thermocouple technique and molecular beam spectrometry, detailed flame structures of PMMA and PMMA+10%TPP were measured. From the experiments and quantum chemistry calculations, the retardancy capability of TPP on gas-phase reaction is proposed. Addition of flame retardant (10%, 20% TPP) results in reduction of the flame spread rate, the mass burning rate and conductive heat flux from the flame to the polymer surface. Numerical calculation was carried out to simulate the downward flame spread over PMMA and PMMA-TPP slabs. Based on the assumption of the TPP gas phase retardancy performance, a modified one-step reaction rate constant with pre-exponent dependent on the TPP mass content in the polymer and TPP retardancy effectivity is proposed. The predicted results have been compared with the data from sophisticated experimental measurement on thermal and chemical structures of both PMMA and PMMA+TPP flames.