Abstract: The structural and electronic characteristics of epitaxial graphene films grown by thermal decomposition of the Si face of a semi-insulating 4H-SiC substrate in an argon environment have been studied by a large set of analytical techniques. It is shown that the results of a complex study make it possible to optimize the growth parameters and develop a reliable technology for the growth of high-quality single-layer graphene films. The charge-carrier concentration in the graphene layer was within 7 × 10¹¹–1 × 10¹² cm^–2, and the maximum mobility of electrons at room temperature approached 6000 cm²/(V s).