Microstructure and optical properties of glass-nanocomposites of compositions xCdI 2 –(1−x)(0.60Ag 2 O–0.40V 2 O 5 )(x=0.0–0.20) have been reported in this paper. X-ray diffraction patterns show the amorphous nature for the compositions x=0 and 0.05. However, nanocrystalline phases have been observed in these compositions in electron microscopic studies. X-ray diffraction and electron microscopic studies reveal formation of different nanocrystalline phases such as β-AgI, Cd 2 V 2 O 7 , Ag 4 V 2 O 7 distributed within the amorphous matrix for the compositions x=0.05–0.20. The presence of Cd 2 V 2 O 7 and β-AgI phase for x=0.05–0.20 confirms the exchange of coordination between Cd and Ag in these samples. The crystalline volume fraction increases with the increase of CdI 2 content in these compositions. The average size of the nanocrystalline phases was estimated from the transmission and scanning electron microscopic studies. The network structure of the glass nanocomposites has been studied using Fourier transform infrared spectroscopy. Differential scanning calorimetric results show that the embedded nanocrystals decrease the glass transition temperature.