The (60-χ)Bi2O3-χTeO2-30B2O3-10ZnO(χ]5,10,20,30, mole fraction) with Eu3+ doped in 1% were fabricated by melting method. The differential thermal analysis (DTA) curves, emission and excitation spectra of the glasses 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 and Ω4 increase with the increase of GeO2 contents. It suggests that the symmetry becomes lower, the band of Eu and O atoms becomes stronger and the covalency increases. The glass transition temperature (Tg) increases with increase of GeO2 content. When the content of GeO2 is about 10%, the different temperature between the glass transition and the crystallization onset temperature, about 146 ℃, reaches the biggest among the samples, indicating that the glass has the best thermal stability.