Abstract An electrochemical adsorptive stripping approach is presented for the trace measurement of copper in some real samples. The method is based on the reduction of Cu 2+ at pH 5.5 calcein blue (CB) containing solution at −250 mV (vs. Ag/AgCl), adsorption of CuCB complex on hanging mercury drop electrode (HMDE) and the voltammetric determination by further reduction to Cu + at HMDE. Experimental optimum conditions were determined in the fundamental studies. At the experimental optimum conditions the adsorbed complex of Cu 2+ and calcein blue gives a well defined cathodic stripping peak current at −0.135 V, which has been used for the determination of copper in the concentration range of 0.02 to 15 ng/mL with accumulation time of 90 s. The relative standard deviation ( RSD ) for the determination of 0.5 and 6.0 ng mL −1 were 2.60 and 1.94% respectively. ( n =10). The method has been applied to the analysis of copper in analytical reagent grade salts and tap water, mineral water and drug samples with satisfactory results.