The absorption,emission,excitation and phonon-side band spectra of Eu³⁺ doped in 1mol(60-χ)Bi₂O_3-χTeO₂-30B₂O₃-10ZnO(χ=5,10,20,30,molar percent) were measured. The Ω₂ and Ω₄ parameters of Eu³⁺ for optical transition were calculated from their emission spectra in terms of reduced matrix U^(t)(λ=2,4,6) character for optical transitions. The results indicate that the intensity parameters Ω₂ decrease as the increase of Bi₂O₃ and decrease of TeO₂ contents. It suggests that the symmetry becomes higher,the bands of Eu and O atoms become weaker and the covalency of Eu and O atoms decreases. In the meantime,the electron-phonon coupling becomes weaker and the thermal stability of the glasses enhance obviously as the increase of Bi₂O₃ and decrease of TeO₂.