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The subsolidus phase relations of the system Gd(2)O(3)-Li(2)O-B(2)O(3) are investigated by means of X-ray diffraction (XRD) analyses. There are eight binary compounds and two ternary compounds in this system. The phase diagram comprises thirteen three-phase regions. The ternary compound Li(6)Gd(BO(3))(3) is refined from the powder XRD data by the Rietveld method. It has a monoclinic structure with cell parameters a=7.2277(2) Angstrom, b=16.5057(5) Angstrom, c=6.6933(2) Angstrom, beta=105.3737(10)degrees and space group P2(1)/c. The rationality of the Li(6)Gd(BO(3))(3) structure is examined by the Brown theory and IR spectra. (C) 2002 Elsevier Science B.V. All rights reserved.