In this paper we report on the in situ synthesis of photo luminescent and patterned polyvinyl chloride (PVC) films, doped with cerium chloride. The precursor of the doping agent is the Tris(2-4 pentanedionate)cerium(III)3H2O, Ce(acac)3, which absorbs UV and visible light. The PVC is both the photochemical source of chloride ion and the rigid matrix where the CeCl3 luminescent particles are dispersed. The PVC films containing cerium complex in the concentration range 0–3% w/w did not exhibit luminescence over 320 nm. After irradiation at 254 nm, the films of pure PVC exhibited luminescence emission with a maximum at about 420 nm, by excitation at 300 nm, due to the presence of polyenes, likely formed by PVC photodehydrochlorination. In PVC films, containing cerium complex, the HCl photoproduct underwent substitution of acac−, with the formation of CeCl3 and Hacac, detected by XPS and FTIR …