In this paper, Er3+ doped TeO2-ZnF2-BaF2-KF-Ta2O5 tellurite glasses with low hydroxyl content (∼0.03 × 10−19 cm−3) were investigated employing both glass composition and glass melting process optimization. The Raman spectra and physical properties were characterized to analyze the structure of the glasses. Under the pumping of 980 nm LD laser, intense up-conversion fluorescence at 1.5 and 2.7 μm of samples and their lifetimes were detected and analyzed, and the related transition mechanisms with gradient-varying Er3+ doping concentrations were discussed. The maximum absorption and emission cross section at 2.7 μm was calculated to be 6.4 × 10−21 cm2 and 6.8 × 10−21 cm2, correspondingly, which were higher than those of traditional tellurite glasses. Using the calculated and measured spectroscopic parameters of bulk tellurite glass, a dual-wavelength pumping model was established to verify the feasibility of mid-infrared laser output in similar tellurite glass fiber. Experimental results support the assertion that the Er3+ doped tellurite glasses hold promise as a candidate laser gain medium for mid-infrared fiber laser systems. © 2023 Elsevier Ltd and Techna Group S.r.l.