The influence of CaTiO3 content on the piezoelectric and photoluminescence performance of the 0.3 mol% Pr-doped NBT-xCT (x = 0, 0.02, 0.04, 0.06, 0.08) ceramics was investigated. The results show that the NBT-xCT: Pr ceramic with x = 0.04 achieves the optimized photoluminescence and piezoelectric properties. A bright red emission at 610 nm and enhanced piezoelectric response are achieved in the ceramics at room temperature. Furthermore, the results show that the photoluminescence performance of the ceramics can be enhanced greatly by poling. The present study opens a way to enhance the photoluminescence of rare-earth doped ferroelectrics. (C) 2012 Elsevier B. V. All rights reserved.