Anhydrous crystalline powders of MnV2O6 (brannerite) were successfully precipitated from mixed aqueous solution of Mn(CH3COO)(2) and V2O5 with a metal ion concentration of 0.01-1.0 mol/l at 135-200degreesC under autogenous hydrothermal condition in a closed vessel. The characterization of MnV2O6 synthesized was carried out by XRD, TG, TEM and anodic performance measurement. In case of mixtures with a concentration of 0.1-1.0 mol/l, single phase anhydrous crystalline MnV2O6 with homogeneous thin rod-like particles were synthesized by autogenous hydrothermal process, though starting reagent V2O5 was not fully dissolved. They showed high anodic performance in lithium ion batteries; high charge capacity as 600 mA h/g even after the 10th cycle and stable cyclic performance. MnV2O6 powders synthesized from relatively high concentration of metal ions showed an abrupt increase in charge capacity after third or fourth discharge/charge cycles, though the first cycle showed rather high irreversible capacity. (C) 2003 Elsevier Science B.V All rights reserved.