AbstractMid‐infrared lasers have important applications in infrared countermeasures, sensing, environmental monitoring, biomedicine, and many military and civilian fields. In this work, an intense emission at 2.9 μm from Yb3+/Ho3+ co‐doped TeO2‐Ga2O3‐ZnO (TGZ) glass was reported. The 2 μm, 1.2 μm and visible emissions were also performed to understand the competitive luminescent mechanism. With the increase in Yb3+ concentration, all the emissions of Ho3+ increased, whereas the emission of Yb3+ decreased due to the phonon‐assisted energy transfer from Yb3+ to Ho3+. The lifetimes of optimized 3 mol% Yb2O3 and 1 mol% Ho2O3 co‐doped TGZ glass, which has the maximum emission intensity, are 548 μs and 1.7 ms at 2.9 and 2 μm, respectively. The Judd–Ofelt intensity parameters, absorption, and emission cross sections were calculated to evaluate the mid‐infrared fluorescence properties of this new glass matrix material. The gain coefficients show that the 2 and 2.9 μm laser gain can be realized by small pump energy, indicating that this glass is a promising medium for the mid‐infrared optical fiber laser.