Near interfaces between two different media exposed to high-energy electron beams substantial dose and fluence perturbations due to backscatter can be observed. In this work, dose and fluence perturbations were studied for 4-19 MeV electron beams at backscatter interfaces of polystyrene, graphite, water, aluminium and lead. Measurements of relative dose using an NPL-designed thin-window plane-parallel ion chamber and a Markus ion chamber were performed to determine the effect of different interface materials and thicknesses. Results of Monte Carlo simulations with the EGSnrc code, including models of the ion chambers, were found to be in excellent agreement with the measurements. The well-documented increasing dose perturbation with increasing effective atomic number of the backscatter material and decreasing electron beam energy was confirmed. Simulations in a simplified slab geometry showed that, despite the decrease of average electron energy with depth in water, the dose perturbations decrease with increasing depth of the interface in water for all the materials in the study. This was ascribed to the change of the electron angular distribution with depth which has a different effect in water and in the presence of a high-Z interface. Electron fluence perturbations near a lead/water interface were found to cause small differences in unrestricted mass collision stopping power ratios, water to air. Effects of bremsstrahlung photons, characteristic photons and positrons from the backscattering material were found to be insignificant for electron interface dosimetry. When comparing simulations using EGSnrc and the older version of the same code, EGS4, underestimations of the dose perturbation effects of up to 7% were found when using the latter code to simulate 4 MeV electrons irradiating a lead/water interface. It is concluded that EGSnrc is a highly suitable tool for electron interface dosimetry studies.