Li2O–ZrO2–SiO2 glasses have been synthesized and subsequently crystallized with different concentrations of CuO (0 to 0.3 mol % in the steps of 0.05) as nucleating agent. The X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) studies have been carried out to explore the influence of copper valence states and their coordination with oxygen on structural and optoelectronic aspects of the samples and to examine the suitability of these materials for optically operated devices. XRD pattern revealed the presence of clear peaks at 2θ = 31.34o and 36.59o corresponding to LiCuO2 orthorhombic crystal phase. SEM indicated that the samples contain well defined, randomly distributed crystals of different sizes ingrained in glassy matrix. FTIR revealed the presence of various bands due to bridging of oxygen perpendicular to Si–Si axis within the Si−O−Si plane.