The energy characteristics of carbyne-containing films on copper and silicon substrates have been studied using the methods of optically stimulated electron emission (OSEE) and ambient pressure photoemission spectroscopy (APS). The average contact potential difference and the work function were determined, and the positions of the Fermi level for carbonaceous films of various thicknesses were calculated. It was found that the electron work function and the position of the Fermi level of the studied film samples are independent of the film thickness and the type of substrate. The information capabilities of the OSEE and APS methods for assessing the quality of carbon coatings on various substrates are shown.