In this work, a semi-empirical pyrolysis model is developed to predict the thermal decomposition behavior of an intumescent fire retardant (IFR) system consisting of ammonium polyphosphate/pentaerythritol (APP/PER) with the ratio 3:1 (wt/wt) in a low-density polyethylene (LDPE) matrix. This work is based on a previously developed semi-global reaction mechanism for the degradation of LDPE and APP/PER, which consists of two consecutive first-order reactions for the LDPE and five first and second-order reactions for the APP/PER combination. The apparent properties that define heat transport inside the pyrolyzing solid are determined via inverse modeling of cone calorimeter experiments for the pure LDPE and then for the complete IFR system. This is achieved by using the Shuffled Complex Evolution optimization algorithm. The flame heat flux in the cone calorimeter experiments is also evaluated by targeting the heat release rate (HRR) data in the optimization process of one of the cone radiative heat setups. The optimized parameters and flame heat feedback are in line with the literature and the robustness of the model is assessed by a comparison with the experimental data for a wide range of cone heat fluxes. Ignition times and peaks of HRR and total HRs are within the engineering accuracy whatever the flux conditions for both pure LDPE and the IFR system.