Hydrogen-bonding interactions involving 2-(trifluoromethyl)-1,1,1,3,3,3-hexafluoropropane (1H) and 1(-) have been quantitatively studied by means of Fourier transform ion cyclotron resonance spectrometry. The existence of the species (1HCl)(-) and (1H1)(-) was demonstrated, and their thermodynamic stabilities were determined experimentally and computation ally. In addition, some of their structural features were analyzed.