A lithium bismuth phosphate, Li2Bi14.67(PO4)(6)O-14, has been synthesized for the first time by the solid-state method. The crystal structure was determined by single crystal X-ray diffraction at 150 K. Li2Bi14.67(PO4)(6)O-14 crystallizes in the monoclinic system C2/c (No. 15), with a = 30.8189(4) angstrom, b = 5.2691(3) angstrom, c = 24.5302(3) angstrom, beta = 122.84(2)degrees, V = 3346.81 (1) angstrom(3) and Z = 2. The structure along the b axis consists of layers of [Bi2O2] units as the basic building block. These are separated by isolated PO4 and UO4 tetrahedra. The oxygen co-ordination around two of the phosphorus atoms is disordered. Solid-state Li-7 NMR studies confirm the presence of lithium in the structure. The material shows ionic conductivity of the order of 10(-5) S cm(-1) at 600 degrees C. (C) 2007 Elsevier Ltd. All rights reserved.