The experimental thermodynamic of MgB2 synthesis process and phase compositions have been investigated by diffraction thermal analysis (DTA) technology and X-ray diffraction. The fabrication of MgB2 bulks and superconducting properties at the temperatures range from 600 to 800°C were reported. And microstructure of MgB2 bulks were observed by scanning electron microscope (SEM). A method was developed to determine the porosity of MgB2 and the highest density can be obtained in MgB2 prepared at 650°C at ambient pressure. It is found that the vapor pressure of Mg increases remarkably at high temperature, leading to the high porosity in MgB2 samples. MgB2 bulk with good superconducting property and fine microstructure was synthesized at 750°C.