BaO-TeO2 glasses containing 10 to 20-mol% BaO were studied by X-ray diffraction, density, thermal analysis, UV–visible and Raman spectroscopy. The effects of Eu3+, Dy3+, Er3+ and Nd3+ on the density, thermal, optical absorption and luminescent properties of barium tellurite glasses were studied. The short-range structure of barium tellurite glasses consists of TeO4 trigonal bipyramidal and TeO3 trigonal pyramidal units. TeO co-ordination (NTeO) was determined by Raman studies; it was found that that NTeO decreases with increase in BaO and rare earth oxide concentration. The glass transition temperature is a function of both the average single bond enthalpy and non-bridging oxygen concentration in the glass network. Glasses containing Dy3+ and Eu3+ show strong visible light photoluminescence, and our results show that barium tellurite glasses are suitable hosts for rare earth ion luminescence due to low phonon energies.