The reaction between BrCN and CF₃CH₂OH in the presence of Et₃N has been investigated in acetone and ether solvents. Three different products have been isolated in the reaction, CF₃CH₂OCN (1), the novel molecule (CF₃CH₂O)₂CNH (2), and Et₂NCN. The product ratio is observed to depend strongly on (i) the solvent used, (ii) the ratio of the reagents, and (iii) the speed of the addition of Et₃N to the reaction mixture. By varying these factors, either 1 or 2 can be obtained as the major reaction product. CF₃CH₂NCO (3) is generated in the gas phase by thermolysis of 2 and Ph₂NC(O)NHCH₂CF₃ precursors. 1, 2, and 3 are characterized in the gas phase by infrared, 2 in the liquid state by Raman, and 1 and 2 in solution by NMR spectroscopies for the first time. The molecular geometries and energetics of the possible conformers are obtained from DFT calculations at the B3LYP level of theory. The observed vibrational frequencies are compared with the results of the DFT calculations, supporting the identification and assisting with the assignments.