By electro-chemical and X-ray graphical analysis it was found out that natrium-vanadium bronze including electronic and plasticity components after thermal treatment changes its structure fully with the formation of combination of lower degrees of vanadium oxidation. The structure of formed combinations has been identified. Chemical vanadium analyzes phase scheme has been worked out in oxidation degree +3, +4, +5 in a joint presence. X-rays analysis data has been confirmed by chemical analysis phase.