We have studied changes in the absorption, temperature, ultraviolet (UV) spectrum, birefringence, and surface profile of various high‐purity ‘‘UV‐grade’’ fused silica samples during KrF excimer laser irradiation at 400 mJ/cm2 and 300 Hz and up to a total of 60 million pulses. All samples exhibit permanent and irreversible changes in the spectroscopic and physical properties. Some samples show a partial ‘‘self‐annealing’’ behavior during the irradiation in which the absorption first increases to a peak value of ∼10%/cm, and then decreases and levels off at a lower value. This may indicate the formation of a new stable state. The radiation‐induced effects are significantly affected by the laser repetition rate, annealing, and ambient temperature of the sample. For comparison, crystalline quartz is tested under similar conditions, and is found to be essentially unchanged by the radiation.