Al(N-3)(3) is produced by the stoichiometric reaction between Al(CH3)(3) and excess HN3 at room temperature. The reaction is thought to proceed by the addition of HN3 to Al(CH3)(3) followed by elimination of CH4, repeated three times to produce the fully azidified Al(N-3)(3). The product Al(N-3)(3) is nonvolatile and condenses as a film on the walls of the reaction vessel. The reaction products were observed in the gas phase and in low-temperature argon matrices by FTIR spectroscopy. Ab initio methods were used to compute the geometry and frequencies of Al(N-3)(3), and the results are in good agreement with experimental data. The films produced upon condensation of Al(N-3)(3) contain the Al-N-2 complex and AlN as well as the azide. Heating the films to 400 K removes the azide and the Al-N-2 leaving AlN. This method may be useful as a low-temperature route to the synthesis of AlN thin films.