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In this paper,polystyrene-based monoliths with highly ordered macroporous structure were synthesized by using SiO2 colloidal crystal as template.SEM observation shows that the macropores are highly ordered and are interconnected by small windows.The BET surface area of PS monolith is about 36.17 m2/g.The polymer monoliths can resist 5 MPa pressure,showing high mechanical and compressive strength.