Abstract—Scanning electron and atomic force microscopy, X-ray diffraction, X-ray spectral microanalysis, and diffraction of reflected electrons were used to study changes in the structure, elemental, and phase composition of fullerite–copper films with an atomic metal fraction of 0.5, 1, 2 and 4%, deposited on oxidized single-crystal silicon substrates and subjected to thermal exposure in vacuum at different temperatures (470, 520, 570 and 620 K). It was found that thermal annealing at T = 520 K (t = 1 h) leads to the formation of a nanocrystalline structure with an average structural elements size of 33, 42, 50, and 65 nm for fullerite–copper films with an atomic fraction of metal of 0.5, 1, 2, and 4% respectively. An increase in temperature and annealing time leads to an increase in the size of structural elements and the formation of a new of CuxC60 phase, which belongs to the monoclinic space group P2/m. Electric force microscopy and the four-probe method were used to study changes in the local electrical properties and electrical resistivity of copper-containing fullerite films during vacuum annealing.