In electrochemistry-related research bile acids and phytosterols do not belong among frequently studied compounds, because they are inactive under variety of conditions and electrode materials. In this contribution, several examples of their redox activity including electrochemical reduction of bile acids at mercury and silver solid amalgam electrodes and electrochemical oxidation of phytosterols and bile acids at platinum, glassy carbon and boron-doped diamond electrodes in non-aqueous media are presented.