In order to veritably measure the first peak of hydration heat evolution that has been illustrated important in indicating cement behavior in early hydration, an improved way of water addition into cement in isothermally calorimetric experiment is put forward. The experimental results indicated that: the magnitude of first peak of heat evolution varies from sample to sample, correlation between heat evolution during first peak of heat evolution and initial (as well as final) setting time is unsatisfactory when samples are not classified; while groups of sample classified based on strength grade represent satisfactory correlations, which indicating the existence of close relation between hydration heat evolution in much earlier hydration age and setting property of cement in rather later age. Importance of first peak in hydration heat evolution for understanding cement setting property and reasons for sample classification are also discussed in this paper.