The X-ray diffraction, X-ray photoelectron spectroscopy, IR spectroscopy of chemisorbed carbon monoxide and kinetic data have been employed to determine the active sites of copper-containing catalysts of both dehydrogenation of cyclohexanol to cyclohexanone and aromatization of cyclohexanol to phenol. Two kinds of copper active sites of the cyclohexanol dehydrogenation reaction to cyclohexanone have been revealed (monovalent copper and metallic copper), and it has been shown that monovalent copper is significantly more active than metallic copper, and monovalent copper does not catalyze the phenol formation. At the same time, metallic copper can play the role of active sites not only in alcohol dehydrogenation to ketone but also in aromatization of cyclohexanol to phenol.