In this work, the effect of an excimer laser has been studied for presenting a method for SF6 decomposition and simultaneous formation of a SiF2 layer on amorphous SiO2. Though the excimer laser did not establish a gas phase photodissociation, we have shown that UV photoablation leads strongly to molecular decomposition in the SF6–SiO2 system. Moreover, the dependence of the decomposition process on the exposure parameters such as the wavelength and intensity as well as the gas pressure and the focal point distance from the gas–solid interface has been investigated.