Eu(3+)-activated La2CaB10O19 phosphors with nominal chemical formulae La(2-x)Eu(x)CaB10O19 and La2Ca(1-2x)Eu(x)Na(x)B10O19 were prepared. The luminescence properties under VUV-UV excitation were investigated. Luminescence spectra reveal Eu(3+) ions occupy both Ca(2+) and La(3+) sites in all samples. The O(2-)→ Eu(3+) charge transfer bands (CTBs) and the (5)D0→(7)F0 emissions of Eu(3+) at Ca (2+) site and La(3+) site are identified, respectively. The schematic energy levels for Eu(3+) in two sites were achieved. Luminescence decays of the (5)D0→(7)F0 transitions were measured for both sites.