Single phase of Gd1-xEuxAl3(BO3)(4) (0.05 <= x <= 1) powder sample was prepared by the thermal decomposition of the corresponding nitrates. Their luminescence properties were investigated and compared under ultraviolet (UV), vacuum ultraviolet (VUV), and cathode ray (CR) excitation. The results indicated that the strong red emission of Gd1-xEuxAl3(BO3)(4) (0.05 <= x <= 1) was observed at about 613 nm due to the D-5(0)-> F-7(2) transition of Eu3+, and the maximum emission intensity was obtained at the concentration of x=0.4, 0.1, and 0.05 under 254 nm, 147 nm, and CR excitation, respectively. The relaxation of excitation energy under the three excitation energies was analyzed. The result showed that the direct excitation on Eu3+ was major under UV excitation. Upon CR excitation, the electron-beam mainly excited the host lattice. For VUV excitation, direct excitation on the host and Eu3+ both existed, and the absorbed energy transferred from the host to Eu3+ via Gd3+ in GdAl3(BO3)(4):Eu3+.