This work is devoted to the study of phase transition processes in nanostructured ceramics of the Y2O3/TiO2-Y2TiO5 type doped with carbon nanotubes as a result of thermal annealing, as well as to the assessment of the prospects of the effect of phase composition on photocatalytic activity. By the method of X-ray phase analysis, it was found that an increase in the annealing temperature leads to the formation of the orthorhombic phase Y2TiO5, as well as structural ordering. Based on the obtained UV spectra, the band gap was calculated, which varies from 2.9 eV (initial sample) to 2.1 eV (annealed at a temperature of 1000 °C). During photocatalytic tests, it was established that the synthesized nanostructured ceramics Y2O3/TiO2-Y2TiO5 doped CNTs show a fairly good photocatalytic activity in the range of 60–90% decomposition of methyl orange.