This paper concentrates on the measurement and analysis of laser ablation effect of particularly prepared aerospace material, polycarbosilane (PCS). Laser ablation experiment setup is designed and built, based on a continuous-wave high-power solid-state laser (CWHPSSL). Steel samples with composite PCS coating are prepared. After that, a group of laser ablation experiment is performed. The samples are shot by laser beam with thousands W/cm 2 fluence. The results, including the ablation morphology and temperature data, is shown and discussed. Temperature data gives a good demonstration of thermal protection effect of composite coating, and in the meanwhile the morphological features in the ablated region reveal the principle of PCS laser-proof effect. Theoretical investigation has also been carried out. The temperature field is simulated based on Fourier equation of heat conduction, and the simulation result provides a good demonstration on thermal-proof effect of PCS coating layer during laser ablation process.