Nano- and micro-sized CeO2 surface layers based on titanium alloy TiAl6V4 were obtained by magnetron sputtering with or without subsequent annealing. The structure of the samples was determined using scanning electron microscopy, Auger electron spectroscopy, energy dispersive spectroscopy, and X-ray diffraction. Hardness was measured by sclerometry. A direct linear dependence of the thickness of the surface layers on the deposition time and an extreme dependence, passing through a maximum, on the power are shown. A decrease in hardness with an increase in the thickness of the cerium oxide coating was noted. An increase in surface roughness, delamination and loosening of the surface layer, presumably associated with annealing, were noted. In samples with a surface layer thinner than 715 nm without annealing and 750 nm after annealing, the formation of a sublayer of TiO2, Al2O3, and Ce(VO4) was found, and in annealed samples with a layer length of less than 300 nm, all cerium dioxide reacted with vanadium dioxide to form vanadate.