The influence of the concentration and position of scandium cations on the thermophysical characteristics of optical ceramics based on a solid solution of Y2O3–Er2O3–Sc2O3–Al2O3 oxides with a garnet structure has been studied. It is established that an increase in the total concentration of scandium leads to a decrease in the thermal conductivity coefficient in ceramics. The dependences of the thermal conductivity coefficient on the concentration and position of scandium cations in the garnet lattice are obtained. As a result the decrease in thermal conductivity of ceramics based on yttrium-erbium-scandium-aluminum garnet is due to structural disordering associated with partial substitution of cations in six- and eight-coordinate positions in the garnet lattice.