Monoclinic Li3V2(PO4)(3) can be rapidly synthesized at 750 degrees C for 5 min (MW5m) by using temperature-controlled microwave solid-state synthesis method (TCMS). The carbon-free sample MW5m presents well electrochemical properties. In the cut-off voltage 3.0-4.3, MW5m presents a charge capacity 132 mAh g(-1), almost equivalent to the reversible cycling of two lithium ions per Li3V2(PO4)(3) formula unit (133 mAh g(-1)), and discharge capacity 126.4 mAh g(-1). In the cut-off voltage 3.0-4.8 V, MW5m shows an initial discharge capacity of 183.4 mAh g(-1), near to the theoretical discharge capacity. In the cycle performance, the capacity fade of Li3V2(PO4)(3) is dependent on the cut-off voltage and the preparation method. (C) 2010 Elsevier B.V. All rights reserved.