The electron momentum distribution of detonation nanodiamonds (DND) was investigated by recording electron energy-loss spectra at large momentum transfer in the transmission electron microscope (TEM), which is known as electron Compton scattering from solid (ECOSS). Compton profile of diamond film obtained by ECOSS was found in good agreement with prior photon experimental measurement and theoretical calculation that for bulk diamond. Compared to the diamond film, the valence Compton profile of DND was found to be narrower, which indicates a more delocalization of the ground-state charge density for the latter. Combining with other TEM characterizations such as high-resolution transmission electron spectroscopy, diffraction, and energy dispersive X-ray spectroscopy measurements, ECOSS was shown to be a great potential technique to study ground-state electronic properties of nanomaterials.