Classical amino-functionalized Fe-terephthalate metal–organic framework NH2-MIL-53­(Fe) and its parent framework MIL-53­(Fe) were prepared via simple hydrothermal methods. The catalytic performaces of these two Fe-MOFs were explored for the selective oxidation of H2S. The physicochemical properties of the fresh and used Fe-MOFs catalysts were investigated by XRD, BET, SEM, FT-IR, CO2-TPD, and XPS techniques. It was found that the introduction of amino groups reduces the activation energies for H2S oxidation and endows this catalyst surface with moderate basic sites. As a result, the NH2-MIL-53­(Fe) catalyst displays high H2S conversion and near 100% S selectivity in the temperature range of 130–160 °C, outperforming commercial Fe2O3 and activated carbon. Moreover, a plausible reaction route for H2S selective oxidation over NH2-MIL-53­(Fe) is proposed. This work opens up the possibility of utilizing MOFs as efficient catalyst for desulfuration reactions.