A new lithium cobalt metaphosphate, LiCo(PO3)(3), is reported for the first time, which was discovered during the exploratory synthesis in Li-Co-P-O system by solid state reaction. The structure has been refined by powder X-ray Rietveld refinement method (P2(1)2(1)2(1), a = 8.5398(2) angstrom, b = 8.6326(2) angstrom and c = 8.3520(2) angstrom, Z = 4, R-p = 13.6%, R-wp = 19.4%, R-exp = 17.7%, S = 1.11, chi(2) = 1.23). It is isostructural with LiM(PO3)(3) (M = Fe, Cu). It contains (PO3)(1-) chains with the Co atoms localized in the octahedral sites, bridging four neighboring chains. The magnetic susceptibility measurement showed a typical paramagnetic behavior of high spin of Co2+, following the Curie-Weiss law in the temperature range of 5-300 K. Unlike the olivine type lithium cobalt phosphate, LiCoPO4, Cyclic voltammetry of LiCo(PO3)(3) assembled in the coin-type cell showed no electrochemical activity in the voltage region of 1-5 V versus Li/Li+. (C) 2005 Elsevier Ltd. All rights reserved.