The crystal structure of Li2B3PO8 was determined by X-ray diffraction of a single crystal prepared by slow cooling from 943 K to 873 K. Li2B3PO8 crystallizes in a triclinic cell (space group P1[combining macron], Z = 8). The sheets of [B3PO8](2-) formed by the linkage of triangular BO3 and tetrahedral BO4 and PO4 groups stack along the b-axis direction.