The clinker mineral tricalcium aluminate (C(3)A) determines largely the early hydration characteristics of Portland cement. Therefore, understanding the influence of the polymer on the hydration of C(3)A is contributed to clarify the mechanism of polymer on the early hydration of cement-based material. The hydration environment of C(3)A in Portland cement was simulated by using C(3)A mineral, gypsum (C (S) over bar center dot H2) and calcium hydroxide (CH). The specimens, whose water cement ratio (m(w)/m(c)) was 0.4 and carboxylated styrene-butadiene (SB) copolymer cement ratio (m(p)/m(c)) was 0, 5, 10, 15 and 20%, were cured at 20 celcius/RH90% for 6 h, 12 h, 1 day, 3 days, 7 days and 28 days, respectively. The effect of SB copolymer on the system of C(3)A-C (S) over bar center dot H2-CH was investigated by the combination of isothermal calorimetry, X-ray diffraction (XRD) and environmental scanning electron microscopy (ESEM). It was found that the SB copolymer retards C(3)A hydration and reduces the heat of hydration. The XRD results revealed that addition of SB copolymer inhibits the consumption of C(3)A, delays the conversion of ettringite (AFt) to calcium monosulfate aluminate hydrate (AFm), promotes the formation of hydrated calcium aluminate (C(4)AH(13)), and reduces the crystallinity of AFm.