Sesquioxides of lanthanides, yttrium, and scandium are promising hosts for laser and scintillation materials; however, the crystallization of such compounds is complicated by very high melting temperatures, as well as polymorph transitions. This work reports for the first time the growth of Y2O3 and Y2−xScxO3 crystals by the Vertical Gradient Freezing method from tungsten crucibles, proposing an alternative to extremely expensive rhenium and iridium crucibles. Translucent Y2O3 samples are obtained, and their luminescent and scintillation parameters are evaluated. The main issues of Y2O3 crystallization under the proposed conditions are discussed, as well as ways of enhancing the crystal quality. Finally, polymorph transitions are avoided by decreasing the average radius of the rare earth cation by Y3+/Sc3+ substitution, providing transparent Y2−xScxO3 crystals with a cubic structure.