An experimental and theoretical study of the tautomeric composition of adenine (Ade) in water using Raman spectroscopy is reported. Experimental resonance Raman spectra of adenine at excitation wavelengths of 200, 218, and 266 nm were compared with quantum-mechanical calculations of N(9)H- and N(7)H-adenine tautomers and their cations. Both theoretical and experimental studies of nonresonance Raman spectra (457 nm excitation) of adenine were also performed for comparison. A satisfactory agreement of the calculated results with the experimental data was obtained. The Raman spectra are interpreted, and the basic regularities of the Raman intensity distribution are explained. On the basis of the analysis performed, the tautomeric composition of adenine in water is revealed. It is shown that the Ade-N(9),N(1)H(+) cation is the predominant form and that some neutral forms of Ade-N(9)H and Ade-N(7)H tautomers exist in water at pH 3.