In this Letter, we present detailed absorption and emission data on nanostructured germanosilicate glasses and glass ceramics containing Ga2O3 nanophases and doped with Gd ions. The results show that these systems are suitable hosts for the enhancement of the excitation cross section of rare earth ions via energy transfer from the gallium oxide nanophase with a related quantum yield of 21%. The role of matrix composition and nanostructure morphology on the Gd emission is discussed.