Dimethylgallium azide, Me2GaN3, is luminescent at low temperature as a polycrystalline solid and in frozen organic glasses. The spectra are very similar in the two media. In the polycrystalline solid, Me2GaN3 is a polymer. The solid-state and solution Raman vibrational spectra show no major changes in the vibrational frequencies. The luminophores are probably moderate chain length oligomers in the frozen glass and polymers in polycrystalline solids. The emission is assigned to azide to gallium charge trasfer with some metal-centered contribution.