The photoluminescence properties of Cr-doped PLZT-9/65/35 (Pb0.95La0.09Zr0.65Ti0.35O3) have been studied. The fluorescence spectra consist of two inhomogeneously broadened narrow bands centred at ∼734 and 740nm and a broadband emission with a maximum at ∼1000nm. The two high energy bands have been assigned to the 2E(2T1)→4A2 transition of two Cr3+ defect centres in octahedral site with high/intermediate crystal field strength whereas the near infrared emission is tentatively assigned to the overlapping of the broadband emission of the Cr3+ ions defect centre’s 4T2→4A2 transition and the emission of the Cr5+ ions’2E→2T2 transition.