The electrospinning technique and the hydrothermal method are two well-known ways to fabricate nanostructures effectively for battery applications. Herein we report a novel preparation of beta-Ag0.33V2O5 nanostructures via an electrospinning technique followed by a hydrothermal process. These electrospun-derived materials are composed of single crystalline nanorods with self-limited aggregation verified by XRD, SEM and TEM results. Characterized by electroanalytical techniques, beta-Ag0.33V2O5 nanostructures show an initial high capacity similar to 250 mA h g(-1) and improved cycling stability with a capacity loss of only similar to 1 mA h g(-1) per cycle after 30 runs at a current of 20 mA g(-1). The materials exhibit a moderate capacity drop at higher charge/discharge rates. Not only is this among the best cycling performance reported so far for the silver vanadium oxide (SVO) series, but the novel atomic inter-planar construction and unique nano-morphology demonstrate a promising road to enhance the cycling stability for electrode materials using the electrospinning technique.