It was shown that Ag(or Ag2O)-ZrO2-Y2O3 formation occurs due to the complex process of decomposition and structure transformation of oxide materials and Ag-complexes. Differences in the decomposition temperatures of Ag-complexes, in particular, and their melting temperatures, and the transformation of ZrO2-Y2O3 NPs morphology leads to the creation of composite structure of two types: an Ag-NPs/zirconia matrix and zirconia core/Ag-shell. It was shown that for these composites the temperature is an effective approach for controlling the NPs sizes for both components (Ag clusters and zirconia NPs), the defectiveness of the complex oxide and their optical properties, in particular the photosensitive to visible irradiation range.