Various V2O5 three-dimensional nanostructures are synthesized using a facile template-free hydrothermal method and evaluated for use as supercapacitor electrode materials. As a result, the yolk-shell structure assembled from ultrathin nanosheets shows the best electrochemical performance, with a specific capacitance of 704.17 F g-1 at 1.0 A g-1 and a high capacity retention of 89% over 4000 cycles at 3.0 A g-1. In addition, a continuous three-dimensional porous coralline-shaped carbon is synthesized from osmanthus and has a large Brunauer-Emmett-Teller surface area of 2840.88 m2 g-1. Then, an asymmetric supercapacitor is developed using the as-prepared yolk-shell V2O5 as a positive electrode and the osmanthus derived coralline-shaped carbon as a negative electrode. This exhibits an energy density of 29.49 W h kg-1 at a power density of 800 W kg-1 with a good cycling performance that retains 90.6% of its initial capacity after 2000 cycles at 3.0 A g-1. Furthermore, two cells in series can easily brightly light up a light-emitting diode (3 V), further demonstrating the great potential of the prepared materials for high-performance supercapacitor devices.