The removal of hydrogen sulfide (H2S) is essential in various industry applications such as purification of syngas for avoiding its corrosion and toxicity to catalysts. The design of adsorbents that can bear corrosion of H2S and overcome the competitive adsorption from carbon dioxide (CO2) is a challenge. To obtain insight into the stability and adsorption mechanism of metal–organic frameworks (MOFs) during the H2S separation process, 11 MOF-based materials were employed for H2S capture from CO2. Density functional theory, molecular dynamic studies, and dynamic separation experiments were used to investigate selective H2S/CO2 separation. Most of these MOFs showed one-off high capacity and selectivity to H2S. Complete reversible physical adsorption was proven on Mg-MOF-74, MIL-101(Cr), UiO-66, ZIF-8, and Ce-BTC. Incomplete reversible adsorption occurred on UiO-66(NH2). Disposable chemical reaction happened on HKUST-1, Cu-BDC(ted)0.5, Zn-MOF-74, MIL-100(Fe) gel, and MOF-5. Using breakthrough experiments, Ui...