A Commercial-Off-The-Shelf (COTS) 4H-SiC p-n photodiode (sold as a UV detector) was investigated as detector of electrons (β− particles) over the temperature range 100 °C to 20 °C. The photodiode had an active area of 0.06 mm2. The currents of the photodiode were measured in dark condition and under the illumination of a 63Ni radioisotope β− particle source (endpoint energy = 66 keV). The photodiode was then coupled to a custom-made low-noise charge-sensitive preamplifier to make a direct detection particle counting electron spectrometer. 63Ni β− particle spectra were accumulated with the spectrometer operating at temperatures up to 100 °C. The quantum efficiency of the photodiode as well as the spectrum expected to be detected were calculated via Monte Carlo simulations produced using the CASINO computer program. Comparisons between the simulated and detected 63Ni β− particle spectra are presented. The work was motivated by efforts to apply COTS technologies to develop low-cost space science instrumentation; a low-cost electron spectrometer of this type could be included on a university-led CubeSat mission for space plasma physics and magnetosphere experiments.