The hydrogen bonding behavior of trifluoromethylphenols and their water complexes were investigated using IR-UV double resonance spectroscopy. Both ortho- and meta-trifluoromethylphenols exist in the syn conformer, which is the global minimum in both the cases. The IR spectrum in the O-H stretching region reveals the absence of an intramolecular O-H center dot center dot center dot F hydrogen bond in the syn-o-trifluoromethylphenol, which is in contrast to the results reported in the literature. The water complexes of both o-trifluoromethylphenol and m-trifluoromethylphenol are characterized by formation of O-H center dot center dot center dot O hydrogen bonds between the donor phenolic OH group and the acceptor water molecule. In addition, the o-trifluoromethylphenol-(water)(2) complex was also observed.