The defect structure, spin Hamiltonian parameters (SHPs: anisotropic factors and and the hyperfine structure constants and ), and their compositional dependence of in ( = 5, 10, 20, 30 mol%) glasses are quantitatively analyzed by using the higher-order perturbation formula of octahedral complex with tetrahedral elongation distortion. Due to the Jahn-Teller effect, the group is subjected to tetragonal elongation distortion of varying degrees. , and show nonlinear changes with the concentrations of . When = 10 mol% CuO, the degree of distortion ( ) is the smallest; when = 30 mol% CuO, the degree of distortion ( ) is the largest, which indicates that excessive distortion leads to the appearance of -axis oxygen vacancies and the coordination number of copper ions from six to four. The increasing tendency of the evaluated and reveals decreasing covalency of the whole glass system. Present theoretical studies would be useful to the explore the structural properties and optical applications of glass with different concentrations.