A sequence of Tb3+/Eu3+/Tm3+ co-doped LaAl2.03(B4O10)O-0.54 single-phase phosphor samples have been produced using a sol-gel reaction. A number of properties such as phase composition, crystal structure, luminescence performance and lifetime decay curves were tested and discussed. The energy transfer process in Tb3+/Eu3+ co-doped LaAl2.03(B4O10)O-0.54 phosphors was testified by luminescence spectra and lifetime decay curves. The transfer mechanism is determined to be a dipole-dipole interaction, and the energy transfer efficiency can reach 74.03%. By adjusting the doping ratio of the three ions of Tb3+, Tm3+ and Eu3+, the light emitting region of the phosphor can be adjusted to white light region. When the composition is LaAl2.03(B4O10)O-0.54:0.1 Tb3+,0.06Tm(3+),0.04Eu(3+), the color coordinate is (0.334, 0.331), which is very close to the standard white light (0.33, 0.33). These results make clearly that Tb3+/Eu3+/Tm3+ co-doped LaAl2.03(B4O10)O-0.54 phosphors have potential application value in the field of single-phase white-emitting phosphors.