Electrochemical reduction of chromium (VI) is studied on a gold microelectrode assembly (Au-MEA) using the cathodic voltammetry (VA) technique. The optimum conditions for obtaining the analytical signal of Cr (VI) are chosen. The range of the analyzed concentrations of Cr (VI) are 0.005–0.2 mg/L, and the detection limit is 5 × 10−5 mg/L. Dissolved oxygen, manifold excesses of alkali and alkaline-earth ions, 200-fold excesses of Cr (III), and 10-fold excesses of Fe (III) and Cu (II) do not interfere with determination of 0.005 mg/L Cr (VI). In the presence of anionic surfactants (DDCNa), the signal of Cr (VI) decreases, but the linear dependence on the concentration remains. A rapid technique for determination of Cr (VI) in purified technical water without sample preparation is suggested. The advantage of Au-MEA consists in the simplicity of synthesis, running time, high sensitivity.