Monoclinic Li3V2(PO4)3 can be rapidly synthesized at 750°C for 5min (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 132mAhg−1, almost equivalent to the reversible cycling of two lithium ions per Li3V2(PO4)3 formula unit (133mAhg−1), and discharge capacity 126.4mAhg−1. In the cut-off voltage 3.0–4.8V, MW5m shows an initial discharge capacity of 183.4mAhg−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.