A new method of analysis of PALS spectra of porous materials is proposed. The model considers both the thermalization process of positronium inside the pores and the pore size distribution. The new model is fitted to spectra of mesoporous silica MCM-41 and MSF. The resulting parameters are compared with parameters obtained from fitting the “conventional” models, i.e. a sum of exponential components with discrete or/and distributed lifetimes.