In free standing crystals of Xe, OCS readily dissociates upon irradiation at 248 nm. On continuation of the laser irradiation, a broad emission centered at 346 nm was found to grow, which is assigned to the Xe-S charge transfer exciplex transition in the crystal. The temperature-induced mobility of S atoms is documented: upon warm-up, the intensity of the exciplex emission decreases with concomitant increase of the S 2 (B → X) emission band intensity.