Different mathematical models can describe coal devolatilization as the part of combustion process. Some models are simple, while others are more complex and take into account coal’s complexity and heterogeneity of structure. A chemical percolation devolatilization (CPD) model for describing the devolatilization process of two Serbian lignites from Kostolac and Kolubara open coal mines was studied. Results of the model were compared to devolatilization measurements obtained from two experimental methods - a wire mesh reactor (WMR) and thermogravimetric analysis (TGA). Two coal samples with four different granulations were investigated for each lignite under different experimental conditions (different maximum temperatures and heating rates). Total volatile yields obtained from the WMR and TGA together with results predicted by the CPD model are presented and compared with literature data. For TGA simulation, the CPD model yielded better results in cases where the kinetic parameters obtained under experimental conditions were used rather than kinetic parameters derived from predefined values in the model itself. For WMR, the CPD model predictions of devolatilization were mixed and were dependent on temperature.