A new borate compound NaCa4(BO3)(3):xEu(2+), xCe(3+) co-doped with Eu2+ and, Ce3+ was prepared by combustion synthesis method using rare-earth nitrates, urea, and boric acid as starting materials. The prepared sample was characterized through X-ray diffraction (XRD), scanning electron microscope (SEM), and fourier transform infrared spectra (FTIR). The energy dispersive x-ray spectrometer (EDX) confirmed the presence of the Na, Ca, B, O, Eu, and Ce. The photoluminescence (PL) excitation and emission spectra of the Eu2+, Ce3+ co-doped NaCa4(BO3)(3) were also investigated using spectrometer at room temperature. The excitation spectrum consists of an intense band peaking at 352 nm. The emission spectrum shows a single intensive band centered at 445 nm, which correspond to the 4f(6)5d(1) -4f(7). For the excitation wavelength of 352 nm the emission intensity increases intially with the increase of lanthanide concentration and reaches to the maximum at x = 0.05 nm. The critical distance of concentration quenching, the luminescence lifetime have also been investigated.