A nanostructured gold modified glassy carbon electrode (Aunano/GCE) was employed for the determination of trace chromium(VI). To prepare Aunano/GCE, the GCE was immersed into KAuCl₄ solution and electrodeposition was conducted at the potential of -0.4 V (vs Ag/AgCl) for 600 s. Scanning electron microscopy measurements show that the electrochemically synthesized gold nanoparticles were deposited in aggregated form. Any undue effects caused by the presence of foreign ions in the solution were also analysed to ensure that common interference in the determination of chromium(VI) by square wave voltammetry, do not influence the electrochemical response of the latter element. The results show that this method allows for Cr(VI) determinations with a much lower detection limit (0.01 𝜇g $L^{-1}$) in the presence of excess of Cr(III) than the commonly used diethylenetriammine pentaacetic acid (DTPA) method. The method was applied to determine levels of chromium(VI) in tap water and sewage water.