2-(2-Cyano-1-ethylthioethenyl)pyrroles easy exchange their ethylthio group for hydroxyl (NaOH, H 2O–methanol, 40–45 °C, 1 h) to give 2-(2-cyano-1-hydroxyethenyl)pyrroles, a new family of stable enols, in 50–94% yields. The vinylic nucleophilic substitution proceeds at the double bond of both the starting pyrroles and their cyclic isomers, 3-iminopyrrolizines. X-ray structure analysis and NMR spectra show the enols to be stabilized by exceptionally strong intramolecular H-bonding.