We report the NH4+ intercalated V2O5, i.e. (NH4)(2)V10O25 center dot 8H(2)O, with excellent electrochemical performance as cathode in aqueous zinc-ion battery (ZIBs), as compared to V2O5, Na5V12O32 and K2V8O21. This work reveals that the ionic conductivity of Zn2+ can be enhanced by introducing cations into the V2O5 framework and the vanadium oxygen structural units will be rearranged. Compared to a single layer of vanadium pentoxide consisting solely of VO5 units, the electrochemical performance of the structural units rearranged vanadates shows a significant improvement. As a result, the obtained (NH4)(2)V10O25 center dot 8H(2)O delivers high discharge capacity (376 mA h g(-1) at 0.5 A g(-1)), superior rate capability up to 10 A g(-1), excellent cycling stability (a capacity retention over 93% for 1000 cycles) and high energy density (341 Wh kg(-1)). (c) 2019 The Electrochemical Society.