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The Cyclic Voltammetric behaviour of copper(II)tetramethylethylenediamine systems with [Cu(II)]:[tmen]=1:10, 1:100 molar ratios, 1×10-3M Cu(ClO4)2.6H2O in aqueous 0.2M NaClO4 supporting electrolyte have been studied at pH5.0,6.50 7.20,9.10, 10.30, 10.85 and 11.20. The electrode process show quasi reversible one electron charge transfer preceded and followed by chemical reaction at glassy carbon electrode (GCE). For a given [Cu(II)]:[tmen] molar ratio, Epc1 increases cathodically with pH. However, at a given pH, and at a given ligand ratio, Epc1 shifts anodically contrary to expectation in the order 1:10 1:100 indicating that the order of stability of complex species follows the same trend.