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We report the preparation of hexagonal mesoporous silica from single-source giant surfactants constructed via dihydroxyl-functionlized polyhedral oligomeric silsesquioxane (DPOSS) heads and a polystyrene (PS) tail. After thermal annealing, the obtained well-ordered hexagonal hybrid was pyrolyzed to afford well-ordered mesoporous silica. A high porosity (e.g., 581 m2/g) and a uniform and narrow pore size distribution (e.g., 3.3 nm) were achieved. Mesoporous silica in diverse shapes and morphologies were achieved by processing the precur