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This paper reports nanostructure of the hydrated Portland cement with ultra low water to cement ratio(W/C).A group of32hardened cement compacts with different W/C was prepared by a method named compact-capillary absorption; bound water was measured to characterize hydration degree of the cement in the compacts; nanostructure of the compacts was investigated by Mercury Intrusion Porosimetry(MIP)and Synchrotron Small Angel X-Ray Scattering(Synchrotron SAXS).