X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy dispersive X-ray spectrometry (EDS), differential scanning calorimetry (DSC), infrared (IR), Raman, electron paramagnetic resonance (EPR) and optical absorption studies on 10Li 2 O–xP 2 O 5 –(89−x)TeO 2 –1CuO glasses (where x=5, 10, 15, 20 and 25mol%) have been carried out. The amorphous nature of the glasses was confirmed using XRD and FESEM measurements. The glass transition temperature (T g ) of glass samples have been estimated from DSC traces and found that the T g increases with increasing P 2 O 5 content. Both the IR and Raman studies have been showed that the present glass system consists of [TeO 3 ], [TeO 4 ], [PO 3 ] and [PO 4 ] units. The spin-Hamiltonian parameters such as g ∥ , g ⊥, and A ∥ have been determined from EPR spectra and it was found that the Cu 2+ ion is present in tetragonal distorted octahedral site with dx2−y2 as the ground state. Bonding parameters and bonding symmetry of Cu 2+ ions have been calculated by correlating EPR and optical data and were found to be composition dependent.