Using a sol-gel method, SmMeOx/MCM-41 or SBA-15 (Me=Fe, Co and Zn) and corresponding unsupported sorbents were prepared. The desulfurization performance of these sorbents was evaluated over a fixed-bed reactor and the effects of reaction temperature, feed and sorbent composition on desulfurization performance were studied. Samarium-based sorbents used to remove H2S from hot coal gas were reported for the first time. The results of successive sulfidation/regeneration cycles revealed that SmFeO3/SBA-15 sorbent was suitable for desulfurization of hot coal gas in the chemical industry. The formation of elemental sulfur during both sulfidation and regeneration processes depended strongly on the catalytic action of Sm2O2S species, which was confirmed for the first time via high sensitive time of flight mass spectrometer (TOF-MS) using 6%vol(18)O2/Ar regeneration gas and can reduce markedly procedural complexity. The sorbents were characterized using N2-adsorption, high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), temperature-programmed reduction of H2 (H2-TPR), thermogravimetry (TG) and time-of-flight mass spectrometry (TOF-MS) techniques.