Azidotris(trifluoromethyl)germane, (CF3)(3)GeN3, was prepared from activated silver azide and iodotris(trifluoromethyl)germane in a neat reaction or in dichloromethane or toluene solution, respectively. (CF3)(3)GeN3 is a colorless, highly volatile liquid (mp ca. -85 degrees C) which was identified from MS data. The new compound was characterized by multinuclear solution NMR (C-13, N-14, F-19) and gas-phase IR spectroscopy. The structure and the vibrational spectrum of (CF3)(3)GeN3 were computed employing density functional theory calculations (DFT) at the self-consistent level with the nonlocal exchange functional of Becke (B) and the nonlocal correlation functional of Lee, Yang, and Parr (B-LYP). The results of the DFT calculation and experimentally obtained vibrational spectra are in good agreement. The DFT computation at the correlated level (B-LYP) predicts the vibrational modes reasonably well, and no scaling was required.