O glasses were made by introducing Cu 2+ as spin probe. The EPR spectra of Cu 2+ in all the glass samples recorded in the X-band frequency have similar spectral features. The variation in glass composition influences the spin Hamiltonian parameters calculated from the spectra. The spin Hamiltonian parameters indicate that the Cu 2+ ions are coordinated with six ligand atoms in a distorted octahedron elongated along one of the axes and the ground state of the Cu 2+ is d x 2 −y 2 orbital. The optical absorption spectra exhibited a broad band corresponding to d-d transition bands of Cu 2+ ion. The values of bonding parameters indicate a covalent nature for the in-plane σ bonding and pure ionic nature for the in-plane and out-of-plane π bonding. The theoretical optical basicity parameter values were evaluated, and it was observed that the value of Γ σ increases whereas Γ π decreases with the increase in optical basicity.