With the increase of cement output, the demand for cement expansion agents increases, and composite expansion agents have become the development trend. The purpose of this study is to study the microscopic change process and expansion effect of calcium oxide and magnesium oxide double expansion agents. After calcination at different temperatures, the change process of microscopic morphology of calcined products was observed. Through calcining dolomite at 900 °C, the mixture D900 of calcium oxide and magnesium oxide was obtained. To prepare mixed cement, 10 wt %, 20 wt %, and 30 wt % of D900 were added into cement to prepare mixed cement. At the same time, the compressive strength, deformation, and porosity of mixed cement were measured. The results show that adding D900 improves the expansion rate of early cement paste and reduces the compressive strength. After 120 days, the compressive strength of 20 wt % cement paste is higher than that of blank cement paste, and the porosity of 20 wt % cement paste is the lowest among the three mixed cements. This shows that 20 wt % is a more suitable substitute.