Experimental studies on the photodissociation of OCS in both crystalline argon and nitrogen are presented. OCS photodissociation is followed by high-resolution interferometric infrared spectroscopy of the CO photoproduct. In solid nitrogen, the photogenerated CO molecule is produced in a damaged site that can be partially healed by thermal annealing. In contrast, the photogenerated CO site in argon does not revert to the sites occupied by neat CO/Ar matrices, even when annealed at 40 K. Model calculations on the infrared spectral line shape and orientational motion of the matrix-isolated CO molecule support a structural interpretation of the experimental findings. The calculations use an Ar-CO intermolecular potential along with an Art pair potential to minimize the energy of a finite section of the full matrix under two broad structural constraints and with both single-and double-substitutional site assumptions. The line shape is calculated via a CO center-of-mass motion weighted perturbation of the isolated CO intramolecular potential by the field of static Ar neighbors.