This work is devoted to generalize and analyze the previouse results of new photonic-crystalline nanomaterials based on synthetic opals and active dielectrics. Data were characterized by X-ray diffraction and Raman spectroscopy. Active dielectrics infiltrated into the pores of the opal from the melt. The phase structure composition of the infiltrated materials into the pores of the opal matrix were analyzed. The results of x-ray diffraction and Raman spectra allowed to establish the crystal state of active dielectrics in the pores of the opal. The Raman spectra of some opal-active dielectric nanocomposites revealed new bands and changes in band intensities compared to the spectra of single crystals of active dielectrics. Further more, differences in band intensities in the spectra were measured at different spots of the sample‘s surface were observed. The revealed changes were attributed to the formation of new crystalline phases due to the injected dielectrics in opal pores.