The effects of Li-doped CaTiO3:Pr3+ thin films have been investigated by varying the lithium ion concentrations from 0 to 5 wt.%. The films have been deposited on Si (100) substrate using a pulsed laser deposition technique. Structural properties of these films have been studied by the measurement of their XRD, SEM, and AFM. The variation of Li+ concentration influences the crystallinity and surface morphology of the CaTiO3:Pr3+ thin films. As Li+ content increases from 0 to 1 wt.%. the crystallinity and intensity of emission increases. The dominant emission is from D-1(2)-> H-3(4) transition at 613 nm. The D-1(2) emission quenching has also been observed in highly doped sample and is related to the cross-relaxation process between Pr3+ ions. (C) 2010 Elsevier B.V. All rights reserved.