Clean preparation of V2O3 by one-step molten salt electrochemical reduction of soluble NaVO3

•A clean and sustainable method for V2O3 preparation is proposed by one-step molten salt electrochemical reduction of soluble NaVO3.•The dependence of current efficiency and electricity consumption on cathode structure, NaVO3 content, electrolysis temperature and voltage were studied.•Electroreduction mechanism of soluble NaVO3 to V2O3 is discussed.•The economic evaluation for ferrovanadium production is preliminarily carried out.