A sensitive method for the determination of chromium ion(VI) in complex matrices such as crude oil and sludge is presented based on the decreasing effect of Cr(VI) on cathodic adsorptive stripping peak height of Cu-adenine complex. Under the optimum experimental conditions (pH 7.5 Britton-Robinson buffer, 5 x 10(-5) M copper, 8 x 10(-6) M adenine and accumulation potential -250 mV versus Ag/AgCl), a linear decrease of the peak current of Cu-adenine was observed, when the chromium(VI) concentration was increased from 5 mu g L-1 to 120 mu g L-1. Detection limit of 2 mu g L-1 was achieved for 120 s accumulation time. The relative standard deviations (R.S.D., %) were 1.8% and 4% for chromium(VI) concentrations of 18 mu g L-1 and 100 mu g L-1, respectively. The method was applied to the determination of chromium(VI) in the presence of high levels of chromium(III), in various real samples such as crude oil, crude oil tank button sludge, waste water and tap water samples. Effects of foreign ions and surfactants on the voltammetric peak and the influences of instrumental and analytical parameters were investigated in detail. The accuracy of the results was checked by ICP and/or AA. (c) 2005 Elsevier B.V. All rights reserved.