A technique for stripping voltammetric determination of arsenic on a gold-film electrode (GFE) with a simplified procedure for preliminary reduction of As (V) to As (III) is proposed. A mixed reducing reagent based on sodium metabisulfite and thiosulfate was used to convert arsenic into an electroactive form, allowing complete quantitative reduction to be achieved within 10 min. The GFE was prepared ex situ by electrodeposition of a gold layer on a rotating glassy carbon electrode (GCE) substrate using potentiostatic electrolysis 300 sec from 1 mM HAuCl4 solution at a potential of –300 mV. With the selected optimal parameters of analyte electroaccumulation, the linear range of the arsenic electrodissolution current was observed from 10 to 200 μg/L, the detection limit was 1 μg/L with an accumulation time of 120 s. The effect of the presence of Cu (II), Bi (III), Pb (II), Fe (III), Mn (II), Zn (II), Cl– ions on the arsenic signal was estimated. To eliminate the contribution of interfering influences to the results, a background electrolyte was used, which was a mixture of 1 M acetate buffer and 0.01 M EDTA. To standardize the technique the measurement quality indicators were assessed in accordance with RMG 61–2010. The proposed technique was applied to determine arsenic in natural water, seafood and inorganic materials; the accuracy of the analysis results is confirmed by atomic absorption spectrometry with electrothermal atomization.