A low refractive index, hard SiO2 film was photochemically coated on the surface of slab laser head at room temperature by using silicone oil and a Xe2 excimer lamp. Nd+:glass slab laser produces high power laser because the light is amplified with a repeated total reflection in the laser medium. However, an evanescent wave arises on the total reflection interface, which causes a loss of the light energy. A low refractive index film 2 μm thick is, therefore, needed to prevent this problem. The vacuum vapor deposition method as a dry process and the spin-coating method as a wet process are generally used for making optical thin films. The former method can laminate a hard thin film, but requires temperatures above 500°C, and the thermal denaturation of the optical substrate is unavoidable. On the other hand, the latter method can form a low refractive index thin film, but the produced thin film has a poor adhesiveness and a low hardness. Besides, all these films are inferior in water resistance. We, therefore, formed a water-resistant, hard, and low refractive index protective coating directly on the laser glass surface at room temperature with photochemical reaction by the Xe2 excimer lamp.