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A novel double‐cladding Ho3+/Tm3+ co‐doped Bi2O3–GeO2–Ga2O3–BaF2 glass fiber, which can be applied to a 2.0‐μm infrared laser, was fabricated by a rod‐tube drawing method. The thermal properties of the glass were studied by differential scanning calorimetry. It showed good thermal stability and matching thermal expansion coefficient for fiber drawing when Tx−Tg > 193°C and the maximum difference of the thermal expansion coefficient is 3.55 × 10−6/°C or less. The 2.0‐μm luminescence characteristics were studied using the central wavelength of 808 nm pump light excitation. The results show that when the concentration ratio of Ho3+/Tm3+ reaches 0.5 mol%:1.0 mol%, the maximum fluorescence intensity was obtained in the core glass, the emission cross section reached 10.09 × 10−21 cm2, and the maximum phonon energy was 751 cm−1. In this paper, a continuous laser output with a maximum power of 0.986 W and a wavelength of 2030 nm was obtained using an erbium‐doped fiber laser as a pump source in a 0.5 m long Ho3+/Tm3+ co‐doped glass fiber. In short, the results show that Ho3+/Tm3+ co‐doped 36Bi2O3–30GeO2–15Ga2O3–10BaF2–9Na2O glass fiber has excellent laser properties, and it is an ideal mid‐infrared fiber material for a 2.0‐μm fiber laser with excellent characteristics [ABSTRACT FROM AUTHOR]