AbstractExtensiveab initiomolecular‐orbital calculations were carried out on trifluoromethylamine (TFM) to elucidate changes in geometry and electronic structure upon fluorination. The calculations show that the decomposition of CF3NH2is slightly endoenergetic, and the heats of atomization of CF3NH2and CH3NH2show decreased stability of the species upon fluorination. Characteristic of CF3NH2is a highly polar, strong, short CN bond. More limited calculations were carried out on CF3OH and CH3OH, and the electronic structure of CF3OH is found to be generally similar to that of CF3NH2. The reduced basicity of the fluorinated amine cannot be ascribed to the inductive effect; the enhanced acidity of the fluorinated alcohol reflects the weakening of the OH bond. No evidence leads to a confirmation of the existence of nitrogen–fluorine hyperconjugation in the fluorinated am