The auto efficiently hydration heat arrangement and the non-contacting electrical resistivity device were used to test the thermology effect and the resistivity variation of Portland cement hydration.The structure forming model of Portland cement initial hydration was established through the systematical experiments with different cements, the amount of mixing water and the chemical admixture. The experimental results show that, the structure forming model of cement could be divided into three stages, i e, solution-solution equilibrium period, structure forming period and structure stabilizing period. Along with the increase of mixing water, the time of inflexion appeared is in advance for thermal process of cement hydration and worsened for the structure forming process. Comparison with the control specimen, adding Na2SO4 makes the minimum critical point lower, the flattening period shorter and the growing slope after stage one steeper. So the hydration and structure forming process of Portland cement could be described more exactly by applying the thermal model and the structure-forming model.