Laser-assisted machining is one of the effective way to solve the problems that the hard and brittle materials are difficult to process. In order to study the influence of chosen processing parameters on the pulsed laser-assisted machining of Al2O3 ceramics, a heat conduction model is established to calculate the temperature field distribution of the workpiece under different parameter combinations. According to the softened layer size of Al2O3 ceramics where the temperature is 1000 K or above, appropriate cutting parameters are determined theoretically. Using related laser and cutting parameters obtained by the theoretical calculation, a cutting experiment is performed, removal rate is calculated, surface roughness and morphology of the workpiece are detected, and the relationship between the removal rate and the surface roughness is analyzed simultaneously. The results indicate that using the chosen processing parameters in accordance with the simulated temperature distribution ensures low surface roughness and high material removal rate during pulsed laser-assisted machining of Al2O3 ceramics. It also indicates that the selected parameters through temperature field simulation can effectively guarantee the requirements to process the hard and brittle materials.