Study of the thermal effect, oxygen content and electronic states of elements in ceramics YBa2Cu3O6+x(0.40 greater than or equal to x greater than or equal to 0.50) by differential scanning calorimetry, chemical analysis and voltammetry of solids has showed that the relaxation phenomena observed in closed-on oxygen system connects with redistribution of oxygenic vacancies and it is accompanied by the reorganization of electronic state of copper settled in the chain.