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Abstract We investigated the physicochemicаl properties, structure and optical properties of the Ge25Ga9.5Sb0.5S65: Er3+/Yb3+ glasses. The Judd-Ofelt theory was used to calculate the intensities of the intra-4f electronic transitions of Er3+ ions. We observed the upconversion photoluminescence (UCPL) at 530, 550, 660 and 810 nm under 980 nm excitation. In the Ge25Ga9.5Sb0.5S65: 0.1 at.% Er3+, we found that the Stokes photoluminescence (PL) at the green spectral region excited by the 490 and 532 nm laser is only ≈5 times higher than the UCPL emission under 810 or 980 nm excitation making these materials attractive for UCPL applications. The addition of 0.1–1 at.% of Yb3+ into Ge25Ga9.5Sb0.5S65: 0.1 at.% Er3+ glass reduces the UCPL as well as the Er3+ ≈1.5 μm emission intensity probably due to the reabsorption processes of the excitation light and concentration quenching. However, the observed Er3+: 4 S 3/2→4 I 13/2 (≈850 nm) emission in the Ge25Ga9.5Sb0.5S65: 0.1 at.% Er3+ sample populates the 4 I 13/2 level, which promises the using of this material for the 1.5 μm optical amplification.