Recently, rechargeable aqueous zinc-ion batteries (AZBs) have attracted extensive interest due to their safety, abundance, low cost, and low toxicity. However, aqueous electrolytes require a polymeric binder to prevent dissolution of the active material in addition to its binding properties. This study highlights binder-free, centimeter long, single-crystal, V2O5 nanofibers (BCS-VONF) on carbon cloth, as the cathode material for AZBs synthesized via a simple one-step hydrothermal process. BCS-VONF in 3.0 M Zn(OTf)2 exhibit promising electrochemical performance with excellent capacity retention. Even in the absence of a binder, BCS-VONF were found to be very stable in 3.0 M Zn(OTf)2. They will not yield to the dissolution and detachment of the active material on the current collector. The novel strategy described in this study is an essential step for the development of BCS-VONF on carbon cloth, as a promising cathode material for AZBs.