The performance of the Venus Express (VEX) ASPERA-4 Electron Spectrometer (ELS) is different from the nominal response shown by the ASPERA-3 ELS aboard Mars Express due to machining tolerance. Up to now, the precise mechanism for this was unknown and, therefore, the results of the experimental calibration could not be supported with a theoretical understanding of the fundamental instrument science behind the device. In this study, we show that the difference is due to a misalignment of the inner hemisphere and a widening of the entrance aperture of the instrument. The response of the VEX ELS can be approximated by a combination of a vertical offset of the inner hemisphere of ≈0.6 mm and a lateral offset of less than 0.125 mm, combined with an aperture that is ≈0.54 mm wider than nominal. The resulting K-factor, geometric factor, energy resolution and peak elevation are in good agreement with those observed experimentally. Therefore, we now have a good agreement between both laboratory calibration data and computer simulation, giving a firm foundation for future scientific data analysis.