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Photoluminescence (PL) bands from potassium dihydrogen phosphate (KDP) crystals are studied by time-resolved PL spectroscopy. KDP crystals irradiated at a laser fluence of 11.5 J/cm2 are found to have the highest probability of phosphorus–oxygen hole center defects and the lowest probability of phosphorus-oxygen electric center defects, in contrast to the probabilities of these defects for KDP crystals irradiated at 9.0 J/cm2. The probabilities of these two defects occurring in retired components are found to be intermediate between those for crystals irradiated at the two different fluences. The two types of defects may result from two different mechanisms and may interconvert under certain conditions. Thus, there are differences between the defects in KDP crystals irradiated at a high laser fluence and those in retired components.