Glass-nanocomposites in the system Ag 2 S–Ag 2 O–MoO 3 have been synthesized by quenching of melts. Microstructural studies of the samples have been accomplished using X-ray diffraction, high-resolution transmission electron microscopy and field emission scanning electron microscopy. The formation of glass-nanocomposites and the presence of different crystalline phases, namely α-Ag 2 MoO 4 , Ag 2 Mo 2 O 7 and γ-Ag 2 S dispersed throughout in the glassy matrix have been confirmed from these studies. The formation and growth of different nanocrystalline phases have been studied as a function of composition and heat-treatment time. The effects of variation of Ag 2 S content and heat-treatment on the local network structure within the glassy matrix have been explored using FT-IR spectroscopic study.