Tm 3+ /Yb 3+ -doped alkali-barium-bismuth-tellurite (LKBBT) glasses have been fabricated and characterized. Density, refractive index, optical absorption, absorption and emission cross-sections of Yb 3+ , Judd–Ofelt parameters and spontaneous transition probabilities of Tm 3+ have been measured and calculated, respectively. Intense blue three-photon upconversion fluorescence and near-infrared two-photon upconversion fluorescence were investigated under the excitation of a 980nm diode laser at room temperature. Wide infrared transmission window, high refractive index and strong blue three-photon upconversion emission of Tm 3+ indicate that Tm 3+ /Yb 3+ co-doped LKBBT glasses are promising upconversion optical and laser materials.