Depending on the polarity and protic abilities of the solvent, 2-(2'-pyridyl)pyrrole can exist in either syn or anti rotameric forms. in nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role. (C) 2004 Elsevier B.V. All rights reserved.