There are a number of chemical compounds that readily convert to other isomers when their crystalline structure is lost (e.g., during melting or dissolution). This phenomenon, commonly known as tautomerism, is a subject of intense research. It is an important problem especially in pharmaceutical industry because various isomers of a drug may have different pharmacological activity. Therefore, it is important to find appropriate experimental technique which enables the determination of the isomerization ability of compounds. In this communication, we demonstrate that broadband dielectric spectroscopy (BDS) method has the potential of detection and monitoring of tautomerism of drugs. To investigate the tautomerism phenomenon we have chosen one of the hypoglycemic agents that belong to the class II of sulfonylurea drugs. Based on density functional theory (DFT) calculations we have analyzed two possible tautomerization pathways of glibenclamide. By using BDS as a tool, we show it can detect the conversion between the isomeric forms through time dependence in the dielectric properties. The activation energy (E(a)) of this process is in good agreement with that obtained from DFT analysis. Finally, we discuss the possible effects of tautomerism on basic pharmaceutical parameters such as biological activity or bioavailability in the case of the glibenclamide drug.