The gadolinium-based borate Rb2LiGdB2O6 (RLGBO) single crystals were obtained by the spontaneous crystallization method from the Rb2CO3-Li2CO3-Gd2O3-H3BO3 system. Meanwhile, the polycrystalline powder RLGBO were obtained by solid phase reaction. The analysis of single crystal structure shows that RLGBO belongs to the orthorhombic system, Pbcm space group, with cell parameters of a=7.025 9(3), b=9.610 3(4), c=10.056 2(4) and z=4. Thermal properties indicate that RLGBO is stable below 840 ℃. After 2% Ce3+, 80% Eu3+ and 50% Tb3+ are doped in the RLGBO respectively, the host structure remains unchange. Under ultraviolet (UV) or near-UV light excitation, RLGBO∶Ce3+, RLGBO∶Eu3+ and RLGBO∶Tb3+can emit blue, red and green lights, respectively. The results show that RLGBO is a promising matrix compound for luminescence materials.