Electron Paramagnetic Resonance (EPR) studies at room temperature in the x-band frequencies on xZnO-10Li2O-10Na2O-10K2O-(69-x)B2O3-1CuO (x=0,2,4,6 and 8 mole%) glass systems were reported. The non-linear variation of spin-Hamiltonian parameters with ZnO content indicated the change in the ligand field strength around Cu2+ ions in the host glass. The ground state of Cu2+ ions in the glass is designated as dx2-y2 orbital (2B1g) while the observed symmetry around it is tetragonally distorted octahedral. The molecular orbital coefficients α2, β2 and β12 are evaluated for Cu2+ doped samples. The non-linear variation in the values of parameters indicated mixed alkali effect in the glasses.