The lithium iron thio-phosphate, Li2FeP2S6, Was synthesized, and its electrode property was investigated. The crystal structure was solved as the CdI2-type with P (3) over bar 1m and a = 6.0145(4) Angstrom, c = 6.5600(2) Angstrom. Two thirds of the Cd sites were occupied by Li+/Fe2+ ions with an occupancy of 1/1, and the rest was occupied by (P4+)(2) paired-ion. The residual Li+ ions occupy octahedral sites in the van der Waals gap of the CdI2 structure. Electrochemical oxidation of Li2FeP2S6 gave a potential plateau at ca. 3.0 V This potential was the highest potential among sulfides examined so far. (C) 2003 Elsevier Science B.V. All rights reserved.