GdAl3(BO3)4:Ln3+ (Ln3+:Eu3+, Tb3+, Dy3+) nano-phosphors were prepared by sol–gel method. The structure properties of the phosphors are characterized by XRD, and GdAl3(BO3)4:Ln3+ nano-phosphors have average sizes around 40 nm. The doping concentrations of Eu3+, Tb3+ and Dy3+ ions in GdAl3(BO3)4 nano-phosphors are from 1 to 9 mol% for Eu3+ ions, from 2 to 12 mol% for Tb3+ ions and from 1 to 5 mol% for Dy3+ ions, respectively. The luminescent properties of rare-earth ions doped GdAl3(BO3)4 nano-phosphors are analyzed by the photoluminescence spectra, which prime doping concentration of Eu3+, Tb3+, and Dy3+ ions are at 5, 12 and 3 mol%, respectively. The energy transfers in the luminescent processes of rare-earth ions doped GdAl3(BO3)4 nano-phosphors are discussed.