Pr 3+ doped CaBi 2Ta 2O 9 based bismuth layered-structure oxides were synthesized by a simple solid state reaction method. The photoluminescence properties of the samples were investigated by excitation and emission spectra. Photoluminescence excitation spectra show that the samples have broad blue excitation band located at 430–510 nm, which covers the emission wavelength of commercial blue light-emitting diode (LED) chips. Upon the excitation of 450 nm light, a novel red emission centered at 621 nm of Pr doped CaBi 2Ta 2O 9 makes it useful in the white LEDs. In addition, it was also found that the photoluminescence can been improved by partial substituting Sr for Ca. These Pr 3+ doped CaBi 2Ta 2O 9 based ferroelectrics could possibly be used as a multifunctional material for a wide range of applications, such as integrated electro-optical devices.