[en] This report summarizes a two-year Laboratory-Directed Research and Development (LDRD) program to gain understanding and control of the important parameters which govern the optical performance of rare-earth (RE) doped ceramics. This LDRD developed the capability to determine stable atomic arrangements in RE doped alumina using local density functional theory, and to model the luminescence from RE-doped alumina using molecular dynamic simulations combined with crystal-field calculations. Local structural features for different phases of alumina were examined experimentally by comparing their photoluminescence spectra and the atomic arrangement of the amorphous phase was determined to be similar to that of the gamma phase. The luminescence lifetimes were correlated to these differences in the local structure. The design of both high and low-phonon energy host materials was demonstrated through the growth of Er-doped aluminum oxide and lanthanum oxide. Multicomponent structures of rare-earth doped telluride glass in an alumina and silica matrix were also prepared. Finally, the optical performance of Er-doped alumina was determined as a function of hydrogen content in the host matrix. This LDRD is the groundwork for future experimentation to understand the effects of ionizing radiation on the optical properties of RE-doped ceramic materials used in space and other radiation environments