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Optically transparent materials such as fused silica, quartz crystal, calcium fluoride, and fluorocarbon polymer were etched upon irradiation of organic solution containing pyrene with a conventional KrF or XeCl excimer laser. Threshold fluences for etching were 240 mJ/cm2 for fused silica, 330 mJ/cm2 for quartz crystal, 740 mJ/cm2 for calcium fluoride, and 45 mJ/cm2 for fluorocarbon polymer. These threshold values were remarkably low compared with those of direct ablation by using conventional lasers. Their etch rates remarkably depended on a concentration of pyrene: the etch rate became higher as the pyrene concentration increased. It means that pyrene molecules play an important role in this process. The mechanisms for this process is discussed by cyclic multiphotonic absorption of pyrene in the excited states, thermal relaxation, and formation of super-heated solution. As the results suggest, the process is based on the combination of two physical processes in the interface between the transparent materials and the liquid: one is a heating process by a super-heated liquid and the other is an attacking process by a high temperature and pressure vapor. The mechanism is also referred to thermal properties of materials.