Clinker has long been regarded as a critical factor for cement hydration and solidification.α-C2S and β-C2S in 2CaO·SiO2(C2S) phase and C3S Monoclinic 1(C3S M1) and C3S Monoclinic 3 (C3S M3) in 3CaO·SiO2 (C3S) phase were clearly recorded in the 29Si MAS NMR spectra.The content of C3S phase in the clinker deduced from the fine peak analysis coincides with the phase quantification analysis calculated by the Taylor-Bogue method based on XRF, which also accords to the statistical data in industrial production.NMR provides a proof that C3S M1 and β-C2S phases have a prior reaction in the early age hydration of clinker,and demonstrates that aluminum coordination changes from tetracoordinated 4CaO·Al203·Fe203(C4AF) to hexacoordinated [Ca2Al(OH)6](SO4)0.3·H20(Aft) in one day hydration and changes to the 3CaO·Al2O3·CaSO4·nH2O (Afm) in a seven-day hydration.