Abstract In this paper, Pr doped CaBi 4 Ti 4 O 15 ceramics were prepared by a traditional solid state method. Crystal structure and morphologies of the ceramics were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photoluminescence properties of the samples were investigated by a spectrofluorometer. Three excitation bands are located at wide range of wavelength, which are 300–430 nm, 440–510 nm and 550–570 nm respectively. Upon the excitation of 494 nm light, the samples shows an emission peak centered at 614 nm, corresponding to 1 D 2 → 3 H 4 transition. A 614 nm red emission excited under the wave with long wavelength of Pr doped CaBi 4 Ti 4 O 15 makes it useful in the white LEDs. In addition, it is an intrinsic ferroelectric and piezoelectric material; the enhanced ferroelectric properties were obtained by Pr doping. As a multifunctional materials, Pr doped CaBi 4 Ti 4 O 15 may be useful in white LEDs, sensor, and optical-electro integration.