Electrochemical deposition combine with pulse laser by using the thermal shock effect of laser, which can improve deposition efficiency and processing quality. The copper was deposited by a compound processing of laser and electrochemical in an experimental system established. The mechanism of the electro-deposition with the thermal shock of the laser was analyzed. These forces created by the laser make cathode substrate produce elastic deformation, changing the electrode potential and current density, improved the electro-deposition quality. Through the processing experiment, the effect of deposition efficiency and processing quality under different average laser power density were studied and iscussed. The results show that when the average laser power density between the 100 kW/cm² to 400 kW/cm², the good deposition quality can be obtained. And the maximum deposition rate can be obtained when the average laser power density about 200 kW/cm².