Oroxylum as a traditional Chinese medicine, was used as a green and novel bio-template to synthesize tremella-like Li₃V₂(PO₄)₃/C composite (LVPC) cathode materials by adopting a facile immersion method. The microstructures were analyzed by X-ray diffraction analysis, scanning electron microscopy, and transmission electron microscopy. The electrochemical properties were investigated by galvanostatic charge-discharge experiments. The LVPC revealed specific capacity of 95 mAh·g at 1 C rate within potential range of 3.0-4.3 V. After 100 cycles at 0.2 C, the retention of discharge capacity was 96%. The modified electrochemical performance is mainly resulted from the distinct tremella-like structure.