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 ESR, optical absorption and photo induced second order susceptibility 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. The photo induced second harmonic generation studies with 10 ns Er: glass laser were carried out to examine the suitability of these materials for optically operated devices. The quantitative analysis of the results of non linear optical studies have shown that 0.2 mol % of CuO is the optimal concentration for getting the highest values of second order susceptibility coefficients.