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A novel 'plugs'-containing Al-SBA-15 material (denoted as PAS) was directly synthesized through simultaneous introducing toluene and aluminum precursor into the reaction mixture of traditional SBA-15. Such material not only featured a unique two-step desorption isotherm as conventional plugged SBA-15 synthesized using excessive siliceous precursor, and higher pore wall thickness than that of other analogous materials, but also possessed weak and medium acidic sites, which implied the PAS would offer unusual advantages such as multifunctionality to process a large variety of feed-stocks in acid-involved reaction (e.g. polymerization of tetrahydrofuran) in industrial point of view. In addition, catalytic activity of the PAS was investigated by the tetrahydrofuran (THF) polymerization reaction in the presence of acetic anhydride and compared with Al-doped MCM-41 prepared via conventional direct hydrothermal synthesis. The PAS exhibited good performance on polymerization of THF. Such result could be related to the large pore size and moderate acidic sites.