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Portland cement paste and Portland cement paste blended with fly ash aged 365 days were studied using synchrotron X-ray tomography with the pixel resolution of 0.74 μm at the BL13W1 beamline of the Shanghai Synchrotron Radiation Facility (SSRF).The volume percentage of unhydrated cement cliker and pore structure parameters were extracted and analyzed.Due to image acquisition and processing procedures, as well as the spatial resolution limitation of tomography, the volume percentage of unhydrated cement clinker from tomography was larger than those from backscattered electron imaging (BEI) analysis, and the pore diameter from tomography was larger than those from mercury intrusion porosimetry (MIP) measurement, while the porosity was on the contrary.Sphericity was used to evaluate the connectivity of pores.The reactivity of cement clinker in Portland fly ash cement paste was higher than that in Portland cement paste.Besides, the pore structure of Portland fly ash cement paste was refined and less connected than Portland cement paste.