A new method for laser milling of Al2O3 ceramic based on deteriorative layer controlled is presented in which no assistant gas was used during the laser milling. The new milling technology is developed by means of laser scanning of ceramic surface and forming a deteriorative layer directly. Laser milling parameters are determined through crystal phase’s analysis of the deteriorative layer. The laser milling depth, surface quality, and milling mechanism with different milling parameters were studied systematically on an Nd: YAG CNC laser and multi-layer laser milling experiments were also conducted with optimized processes on the surface of Al2O3 ceramic workpiece. Therefore, the practical experimental results are that each depth of layer milling is between 0.35-0.5 mm and the surface roughness of laser milling reaches to Ra 2-3.2μm. The experimental study has thus provided deeper understanding on laser milling technology for Al2O3 ceramic both in theory and application.