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Identification and quantification of Chemical species participating in electrochemical processes sheds light on the Chemical aspects of electrochemical reactions, thus clarifying their mechanisms. lon-selective microelectrodes are unique tools that enable one to provide information about localized activity of specific ions in solu-tion (e.g. H+, Mg2+, Zn2+, Al3+, Na+ and Cl ). The micro-potentiometric measurements with ion-selective microelectrodes can be performed using SIET and SECM in poten-tiometric modę. The lecture will introduce the basics of micro-potentiometry, dis-close the limitations and pitfalls of SIET and gives an overview with various applica-tion examples essential for materiał science.