A simple and green route for the preparation of CaV2O4 through one-step incomplete electrochemical reduction of soluble NaVO3 in CaCl2 molten salt is proposed. NaVO3 was found to exist in the form of Ca2VO4Cl in the molten salt with VO43- as the reactive ion. CaV2O4 possessing a surface carbon layer and rod structure was obtained by adding CaCO3 during electrolysis. The electrochemical reduction mechanism was also analyzed, and the results indicated that VO43- was incompletely reduced to VO2- at about -1.23 V (vs. Ag/AgCl) by a two-electron transfer process. VO2- ions then combined with Ca2+ to form CaV2O4. Meanwhile, CO(3)(2-)was reduced to carbon in a two-step process. (C) 2019 The Electrochemical Society.