In this study, Zn4B6O13, Eu- and Tb-doped Zn4B6O13 phosphors were prepared by conventional solid state reaction method and the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). The doped rare-earth ions had little influence on the crystal structure of Zn4B6O13, but obviously affected the morphology of Zn4B6O13 particles. The PL results indicated that the 5% Eu-doped sample and 1% Tb-doped sample had the highest intensity in their respective different concentrations doped samples. The CIE chromaticity coordinates indicated that Zn4B6O13, Zn4B6O13:Eu and Zn4B6O13:Tb showed the three basic colors of blue, red and green, respectively. Evidently, the white light could appear only at appropriate intensity of blue, red and green components.