In order to search possible residual minor phases in Y-Ba-Cu-O family, powdered mixtures of Y2O3 + BaCO3 + CuO and, independently, superconducting compound YBa2Cu3O7-x have been treated in evacuated cells and elevated temperatures.YBa2Cu3O7-x was reduced to YBa2Cu3O5 by use of the special home designed Taconis-Knudsen vacuum device. A subsequent doping by oxygen converts produced insulator YBa2Cu3O5 to semiconductor or metal YBa2Cu3O5+x (0<x<0.3). In addition to YBa2Cu3O5, 0.05 volume percent of the minor delafossite phase Y2Cu2O4 was being spotted in the powder mixture 1/2 Y2O3 + 2BaCO3+6Cu2O, heated up to 818 °C in an inert gas atmosphere. An attempt to prepare the insulating bulk delafossite samples was successful, and subsequent doping by oxygen produces novel metallic phases.