This work describes a Monte Carlo algorithm which appropriately takes into account the stochastic behavior of electron transport in solids and the simulation of the energy distributions of the secondary and backscattered electrons from polymethylmethacrylate irradiated by an electron beam. The simulation of the backscattered and secondary electron spectra also allows calculating the backscattering coefficientand the secondary electron yield of polymethylmethacrylate as a function of the initial energy of the incident electrons. Results of the simulation are compared with the available experimental data. The importance of considering all the electrons emerging form the surface in calculating the secondary electron yield and the backscattering coefficient is highlighted. In particular, we will discuss the importance of taking into account the tail of high energy secondary electrons in the spectrum for the simulation of the backscattering coefficient. (C) 2015 Elsevier B. V. All rights reserved.