Rechargeable aqueous batteries are promising devices for large-scale energy-storage applications because of their low-cost, inherent safety, and environmental friendliness. Among them, aqueous ammonium-ion (NH4 + ) batteries (AAIB) are currently emerging owing to the fast diffusion kinetics of NH4 + . Nevertheless, it is still a challenge to obtain stable AAIB with relatively high output potential, considering the instability of many electrode materials in an aqueous environment. Herein, a cell based on a concentrated (5.8 m) aqueous (NH4 )2 SO4 electrolyte, ammonium copper hexacyanoferrate (N-CuHCF) as the positive electrode (cathode), and 3,4,9,10-perylene-bis(dicarboximide) (PTCDI) as the negative electrode (anode) is reported. The solvation structure, electrochemical properties, as well as the electrode-electrolyte interface and interphase are systematically investigated by the combination of theoretical and experimental methods. The results indicate a remarkable cycling performance of the low-cost rocking-chair AAIB, which offers a capacity retention of ≈72% after 1000 cycles and an average output potential of ≈1.0 V.