Investigations for optimization of working electrode potentials, quantity of charge, level of background current and electrolysis time for achieving quantitative reduction of Ga(III) to Ga and its oxidation back to Ga(III), were undertaken. Effect of gallium content and interference of zinc in of gallium determination were also studied. The developed methodology was employed for the determination of gallium in pure Ga as well as in synthetic U+Ga mixture solutions. Accuracy and precision values of better than 0.5% were obtained at 1–2 mg levels.