We have calculated electron backscattering coefficients, η(Ep), at primary electron energies Ep of 0.1–100 keV for three elemental and intermediate atomic number solids, Cr, Co and Pd, with an up-to-date Monte Carlo simulation model. A relativistic dielectric functional approach is adopted for the calculation of the electron inelastic cross section, where several different datasets of optical energy loss function (ELF) are adopted. The calculated backscattering coefficient is found to be substantially affected by the ELF, where the influence can be seen to follow the f- and ps-sum rules and the resultant energy dependence of electron inelastic mean free path. To understand the uncertainties involved in a comparison with experimental data both the theoretical uncertainty due to the elastic cross-section model and the experimental systematic error for the contaminated surfaces are investigated. A total of 192 different scattering potentials are employed for the calculation of Mott's electron elastic cross section and this theoretical uncertainty is confirmed to be small. On the other hand, the simulation of contaminated Co and Pd surfaces with several carbonaceous atomic layers can well explain the experimental data. The present results indicate that accurate backscattering coefficient data should be either measured from fully cleaned surfaces or obtained from modern Monte Carlo theoretical calculations involving reliable optical constants data. With the recent progress in the accurate measurement of optical constants by reflection electron energy loss spectroscopy technique, constructing a reliable theoretical database of electron backscattering coefficients for clean surfaces of elemental solids is highly hopeful.