Experimental low-loss electron (LLE) yields were measured as a function of loss energy for a range of elemental standards using a high-vacuum scanning electron microscope operating at 5 keV primary beam energy with losses from 0 to 1 keV. The resulting LLE yield curves were compared with Monte Carlo simulations of the LLE yield in the particular beam/sample/detector geometry employed in the experiment to investigate the possibility of modeling the LLE yield for a series of elements. Monte Carlo simulations were performed using both the Joy and Luo [Joy, D.C. & Luo, S., Scanning11(4), 176–180 (1989)] expression for the electron stopping power and recent tabulated values of Tanuma et al. [Tanuma, S. et al., Surf Interf Anal37(11), 978–988 (2005)] to assess the influence of the more recent stopping power data on the simulation results. Further simulations have been conducted to explore the influence of sample/detector geometry on the LLE signal in the case of layered samples consisting of a thin C overlayer on an elemental substrate. Experimental LLE data were collected from a range of elemental samples coated with a thin C overlayer, and comparisons with Monte Carlo simulations were used to establish the overlayer thickness.