AbstractThe electrochemical behavior of tolterodine, an antimuscarinic drug used to treat urge incontinence and overactive bladder, was investigated using cyclic and differential pulse voltammetry at glassy carbon electrode. Electrooxidation of tolterodine proceeds as a complex two‐step pH‐dependent process. Controlled potential electrolysis of tolterodine solutions was performed at platinum gauze electrode in methanolic, aqueous‐methanolic and acetonitrile media. Electrolyzed solutions were analyzed using liquid chromatography with electrospray ionization quadrupole time‐of‐flight mass spectrometry. 5‐Hydroxymethyl tolterodine, the main biologically active metabolite of tolterodine, was identified among monomeric oxidation products. Dimeric products, formed by oxidative coupling of phenoxy radicals, were found in all electrolyzed solutions. The mechanism of the electrochemical oxidation of tolterodine has been proposed.