Vanadium trioxide (V2O3) was directly prepared by NaVO3 electrolysis in NaCl molten salts. Electrolysis products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The existing state and electrochemical behavior of NaVO3 were also studied. The results indicated that V2O3 can be obtained from NaVO3. VC and C were also formed at high cell voltage, high temperature, and long electrolysis time. During electrolysis, NaVO3 was dissociated to Na+and VO3- in NaCl molten salt. NaVO3 was initially electro- reduced to V2O3 on cathode and Na2O was released simultaneously. Na2CO3 was formed due to the reaction between Na2O and CO2. The production of C was ascribed to the electro-reduction of CO32-. VC was produced due to the reaction between C and V2O3.