A novel and simple in-situ solid-state reaction route is developed to synthesize a three-dimensional (3D) porous carbon fiber film-supported Li3V2(PO4)3 membrane electrode. The carbon film is obtained via the carbonization of a bioproduct rice paper (RP). The carbon film can function as both a current collector and a 3D electronic conduction network for the loaded Li3V2(PO4)3 particles. The structure and electrochemical properties of the Li3V2(PO4)3 membrane electrode are characterized. As a free-standing membrane electrode, it exhibits good rate performance at room temperature with a specific capacity of 108 and 142mAhg−1 at 10C rate in the voltage range of 3.0–4.3V and 3.0–4.8V, respectively. It also shows good cycling performance with a specific capacity of 123mAhg−1 after 500 cycles at 1C rate in the voltage range of 3.0–4.8V.