This Letter provides a qualitative proof of concept for purposefully tailoring the emission spectrum of glass by spatially localizing dissimilar dopants to control the degree of energy transfer. More specifically, modified-chemical-vapor-deposition-derived silica preforms were solution doped with either a solution of individually Eu(3+)- or Tb(3+)-doped nanoparticles or a solution of Eu(3+)/Tb(3+)-codoped nanoparticles. The preform prepared using the codoped nanoparticles exhibited energy transfer from the Tb(3+) to the Eu(3+) ions, whereas the preform containing individually doped nanoparticles yielded only discretely Tb(3+) or Eu(3+) emissions. The extension of this work to broadband amplifiers and lasers is discussed.