The MgB₂/Mo multilayer films were fabricated, which the MgB₂ layers were grown by using the hybrid physics-chemistry vapor deposited (HPCVD), the Mo films were prepared with Magnetron sputtering (MS) technology. Scanning electron microscopy, X-ray diffraction, and four-point probe method were carried out to study surface morphology, superconducting properties and crystal structure of MgB₂/Mo multilayer. The results addressed the multilayer can maintain good stability which the crystallization degree is further improved and the grain size is increases with the subsequent deposition temperature of MgB₂ films. Excellent properties are obtained in the upper MgB₂ layer prepared at 730℃, including the superconducting transition temperature(T_con) and zero resistance temperature(T_c0) for 39.73K~39.53K,the remaining resistivity down to about 0.77μΩcm, which indicates that films are in the clean limit.