Pr3+-doped (Ba0.85Ca0.15)(Zr0.1Ti0.9)TiO3 ceramics were prepared by a solid-state reaction method. The effects of doping concentration, sintering temperature, and ferroelectric remanent polarization on photoluminescence (PL) properties of samples were systematically investigated. The PL spectra of samples exhibit strong green and red emissions with a broad blue excitation band ranging from 430 to 500nm, in a good agreement with all commercial blue LEDs emission wavelength. Except for the concentration and temperature PL quenching, the polarization-induced PL quenching was obviously observed, and the degree of PL quenching changes with Pr3+ concentrations, the origin of the change is well interpreted by field-induced structural phase transitions between rhombohedral (R3m) and tetragonal (P4mm) for BCZT: xPr ceramics near the morphotropic phase boundary.