A series of Ca3La3((1-x))Ce-3x(BO3)(5) phosphors were prepared by a high-temperature solid-state reaction technique. Rietveld refinement was performed using the powder X-ray diffraction (XRD) data, which shows occupation of Ce3+ on both Ca2+ and La3+ sites with a preferred location on the La3+ site over the Ca2+ site. The prepared samples contain minor second phase LaBO3 with contents of similar to 0.64-3.27 wt % from the Rietveld analysis. LaBO3:1%Ce3+ was prepared as a single phase material and its excitation and emission bands were determined for identifying the influence of impurity LaBO3:Ce3+ luminescence on the spectra of the Ca3La3(1-x)Ce3x(BO3)(3) samples. The luminescence properties of Ca3La3(1-x)Ce3x(BO3)(5) samples under vacuum ultraviolet (VUV) and UV excitation were investigated, which exhibited two-center luminescence of Ce3+, assigned to the Ce(1)(3+) center in the La3+ site and Ce(2)(3+) center in the Ca2+ site, taking into account the spectroscopic properties and the Rietveld refinement results. The influences of the doping concentration and the excitation wavelength on the luminescence of Ce3+ in Ca3La3(1-x)Ce3x(BO3)(5) are discussed together with the decay characteristics.