The present invention belongs to the field of micro-manufacturing. Aiming at the shortcomings of traditional methods, excimer laser, integrated circuit plate-making lithography, electrochemistry and scanning probe microscopic technology are fused into a new processing method. The steps are: (1) first prepare a microscopic probe Needle array; (2) Fix the substrate between the plate electrode and the microprobe array, generate negative pressure, and inject protective gas; (3) Apply voltage between the electrodes after injecting the electrolyte solution, and at the same time pass through the excimer laser The electrochemical reaction is controlled to complete the machining process. The corresponding device is equipped with an electrochemical reaction chamber on the workbench of the laser microprocessing machine, which includes a laser pneumatic window, a protective gas inlet, a vacuum pump interface, an electrolyte solution inlet, a microprobe array, a flat electrode, an auxiliary electrochemical reaction gas inlet, and a waste outlet. . The invention can obtain a microstructure with an aspect ratio of 5-50 and a characteristic size of 1-50 microns on metal and semiconductor substrates, and has wide applications in the fields of environmental protection, textiles, papermaking, energy, information and national defense.