Tautomerism in the ground and excited states of 7-hydroxyquinoline (7HQ) was studied in different solvents using steady-state and lifetime spectroscopic measurements, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations. Equilibrium between the enol and the keto/zwitterion tautomers exists in 7HQ which is solvent-dependent. Of the solvents used in this study, only in water does the absorbance spectrum of 7HQ show absorption from both the enol and zwitterion tautomers. In addition, in aqueous media, fluorescence is observed from the zwitterion tautomer only, which is attributed to self-quenching of the enol fluorescence by energy transfer to the ground-state zwitterion tautomer and energetically favorable excited-state proton transfer. Solvation of the hydrogen bonding sites of 7HQ was studied in binary mixtures of 1,4-dioxane and water, and three water molecules were estimated to connect the polar sites and induce intermolecular proton transfer. The results are confirmed by DFT calculations showing that three water molecules are the minimum number required to form a stable solvent wire. Mapping the water density around the polar sites using MD simulations shows well-defined hydrogen bonds around the amino and hydroxyl groups of the enol tautomer and slightly less well-defined hydrogen bonds for the zwitterion tautomer. The presence of three-member water wires connecting the polar centers in 7HQ is evident in the MD simulations. The results point to the unique spectral signatures of 7HQ in water, which make this molecule a potential probe to detect the presence of water in nanocavities of macromolecules.