This work is devoted to the development of a novel method of gallium purification especially designed for the fabrication of semiconductors and optical materials of UV–Visible-Mid IR range. For the first time gallium was purified by distillation in complex oxygen-hydrogen plasma. The process of purification including both oxidation and reduction stages was carried out at the low pressure (1∙10−3 Torr) in inductively coupled non-equilibrium RF (40.68 MHz) plasma discharge. In situ Optical Emission Spectroscopy (OES) was also used to determine the intermediate excited species forming in the process of plasma-chemical purification. The novel technological approach is aiming to diminish content as metal as carbon-containing impurities that behaviour was also investigated. A possible mechanism of impurities conversion during the process was discussed.