The development of microstructure of cement-based materials should be mainly responsible for the time dependences of their rheological properties. In this paper, a series of structural kinetics constitutive models were established to predict the time-evolutions of the rheological properties of fresh cement paste under different working conditions. The models were developed from the Hershel-Bulkley model by combining a kinetic equation of the structural parameter λ and the relationships between rheological parameters and the structural parameter. The effects of shear rate, thixotropy and cement hydration on the structural breakdown and structural build-up were considered in the kinetic equation. Meanwhile, the specific parameters of Portland cement paste in the kinetic equation were estimated according to the experimental data of published literatures. Moreover, the reliability of the new models was further validated by comparing the experimental results with the predicted value of dynamic and static yield stresses of cement pastes under mixing and rest. Thus, the relationship for Portland cement between the development of microstructure and the rheological properties had been established.