Spectral characteristics of methyl 2-hydroxynicotinate (MEHNA) have been studied using absorption, fluorescence excitation and fluorescence spectroscopy, as well as, using single photon counting nanosecond spectrofluorimeter. MEHNA is present as enol in less polar solvents and keto in polar media. In non-polar solvents, large Stokes shifted fluorescence band is assigned to phototautomer, formed by excited state intramolecular proton transfer (ESIPT), whereas fluorescence is only observed from keto form in polar solvents. In aqueous and polar solvents monocation (MC) is formed by protonating the exo carbonyl oxygen atom in the ground state (S0) and in the first excited singlet state (S1), MC is obtained by protonating carbonyl oxygen atom of the ester. It is formed by ESIPT from exo carbonyl proton to carbonyl oxygen atom of the ester. Dication is formed by protonating both the oxygen atoms. Two kinds of monoanions formed by deprotonating phenolic proton or N-H proton of keto suggest the presence of enol and keto in aqueous solution. In cyclohexane MC is formed by protonating carbonyl oxygen in both S0 and S 1 states. The electronic structure calculations were performed on each species using semi-empirical quantum mechanical AM1 method and density functional theory B3LYP with 6-31G** basis set using Gaussian 98 program, along with potential energy mapping, to characterize the particular species. © 2004 Elsevier B.V. All rights reserved.