[en] Highlights: • Electronic structure of thioamide group and its relation to Lewis basicity. • Tautomerism of the (thio)amide groups. • Substituent effects on the electronic structure of (thio)amide group. - Abstract: The electronic structures of several thioamides have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of thioamide derivatives are discussed. The predominant tautomers in the gas phase are of keto–(thio)keto form. The addition of cyclohexanone moiety to the thioamide group enhances the Lewis base character of the sulfur atom. The addition of phenyl group to the (thio)amide group significantly affects its electronic structure.