In this study, electrochemical experiments were performed in non-aqueous media in order to determine electrochemical behavior of some of the glyoxime derivatives (GDs). Phenylglyoxime (PG), p-chloro-phenylglyoxime (p-CPG), and 1,2-phenylendiamino-p-chlorophenylglyoxime (PACPG) were chosen as GDs. Pt wire, Ag/Ag+ (in 0.01 M AgNO3) and glassy carbon (GC) electrode were used as counter, reference, and working electrode, respectively. The multiscan cyclic voltammograms (CVs) of these compounds were registered in acetonitrile (MeCN) containing 0.1 M tetrabutylammonium tetrafluoroborat (TBATFB) at scan rate of 100 mV/s. The potential was swept from 0 to +2.0 V versus Ag/Ag+ (0.01 M). The CVs of GDs were compared with each other and the electrochemical behaviors of the compounds were investigated depending on the functional groups in their structures. The electrochemical characterization of these modified surfaces was performed and characterizations were compared with the chatacterization results of bare GC surfaces. The application areas for new surfaces were investigated. These results will be active in the disciplines of electrochemistry and industrial physical chemistry, and in related industrial fields at the dissemination of new information for scientific area.Determination of trace metals in waste water is based on the modification of solid electrode surfaces with glyoxime derivatives in order to form effective surfaces. The main force of the here described method is an easy and successfully application to environmental samples. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.