(Received 30 January 2012; Accepted 2 July 2012; Published 25 August 2012)A reverse Monte Carlo (RMC) method is developed in this work to study the energy-loss process of signalelectrons in surface electron spectroscopy. This method derives the effective energy-loss function (EELF) froma measured reflection electron energy loss spectroscopy (REELS) spectrum by an iterative Monte Carlo (MC)simulation procedure other than deconvolution procedure, in accordance with the complicated electron transportprocess. The method combines the Markov chain Monte Carlo (MCMC) sampling (i.e. Metropolis importantsampling) of oscillator parameters with a usual MC simulation of electron interaction with solids, which acts as asingle step of MCMC sampling. To examine the reliability of this method, we have performed a test which leadsto derive the same EELF with different trial inputs of initial oscillator parameters. Calculation results show thatEELF can be pretty well derived by the RMC method even without a proper choice of initial trial parameters. Asan example the EELFs for Ag at different electron energies are derived from the measured REELS spectra by thisRMS method.[DOI: 10.1380/ejssnt.2012.441]