A novel toolkit to quantitatively determine the key parameters that control the flame retardancy of polymeric materials is presented in this paper. A comprehensive review is also presented to support the concept behind the development of this toolkit and to identify these key parameters. The results presented in this paper support the validity of this approach. The present study shows that the determination of parameters such as the surface ignition temperature, the rate of thermal degradation, the total amount of volatiles formed, the chemical composition of volatiles, and finally the distribution of flame-retardant additives such as PFR in the gas and the condensed polymer phase is a powerful tool for the prediction of flame-retarding behaviour of polymer materials and thereby to develop new and more effective halogen free flame retarded formulations.