H-1-NMR measurements of halogenoalcohol-water mixtures were carried out using an exernal reference method, and it is attempted to determine the chemical shift of the water proton from the coalesced peak of water and alcoholic OH protons. The results show that the chemical shift of the water proton shifts to high field with increasing halogenoalcohol concentrations. The high-field shift is found to be dependent not on the size of the alkyl part of the alcohols but on the species and the number of halogen atoms, which leads us to conclude that the breaking of water structure in the mixtures is due to the interaction of water molecules with the halogen group of the halogenoalcohols.