- We, for the first time, demonstrate that orthorhombic V₂O₅ can exhibit superior electrochemical performance in sodium ion batteries when uniformly coated inside nanoporous carbon. The encapsulated V₂O₅ shows a specific capacity as high as 276 mAh/g, while the whole nanocomposite exhibits a capacity of 170 mAh/g. The V₂O₅/C composite was fabricated by a novel ambient hydrolysis deposition that features sequential water vapor adsorption in nanoporous carbon, followed by a hydrolysis reaction, exclusively inside the nanopores. The unique structure of the nanocomposite significantly enhances the capacity as well as the rate performance of orthorhombic V₂O₅ where the composite retains a capacity of over 90 mAh/g at a current rate of 640 mA/g. Furthermore, by calculating, we also revealed that a large portion of the sodium-ion storage, particularly at high current rates, is due to the V₂O₅ pseudocapacitance.