Abstract: The mixture of 4,4’-diaminodiphenyl ether (ODA), 3,3’,4,4’-biphenyltetracarboxylic dianhydride (BPDA) and hydrotalcite were thoroughly ground to get oligomer by solid phase prepolymerized. After polymerized in solvent, the composite of polyimide/hydrotalcite was obtained through thermal imidiation process. The structures and components of composite materials had been characterized by Fourier transform infrared spectroscopy and X-ray diffraction. The thermal property, mechanical property and surface character of the composites had been studied also. The results show that the polyimide/hydrotalcite composites with better dispersed hydrotalcite were gained by this method. And the heat resistance and mechanical performance of the composites were improved when the contents of hydrotalcite in a certain range.