Hexagonally ordered mesoporous MSU-S was assembled from nanoclustered zeolite seeds. The XRD and BET results verified that after treated in 10%H 2 O/N 2 atmosphere at 800°C for 2 h, MSU-S still remained a well-ordered hexagonal structure due to rich acidic sites and excellent hydrothermal stability. A series of Sm x Mn y O z /MSU-S sorbents were prepared by a sol−gel method. The desulfurization performances of the 55%Sm 5 Mn 95 /MSU-S sorbent were improved significantly due to high hydrothermal stability of MSU-S with high surface area as well as the synergistic effect between Mn and Sm 2 O 3 . The result of eight successive sulfurization/regeneration cycles of sorbent illustrated that high breakthrough sulfur capacity and endurable stability of 55%Sm 5 Mn 95 /MSU-S correlated closely with the existence of the framework 4-coordination aluminum (NH 3 -TPD, 27 Al MAS NMR) and high dispersion of Sm/Mn species on MSU-S (XRD, TPR) for H 2 S removal. HRTEM images and SAED patterns confirmed that fresh 55%Sm 5 Mn 95 /MSU-S existed in high ordered mesoporous structure and the nanosized Sm 2 O 3 and Mn 3 O 4 particles occurred in highly dispersive polycrystallites. The valence state of Mn species and the regeneration process of used sorbent were characterized by X-ray photoelectron spectroscopy (XPS) and TG/DSC. In addition, the effects of reaction temperature, feed composition and Sm/Mn atomic ratio in sorbents on desulfurization performance were investigated.