Aqueous zinc ion batteries (AZIBs) featuring low cost and high safety are attracting considerable interest. More recently, ammonium vanadate, characterized by its high specific capacity, is regarded as a promising cathode material for AZIBs. However, their unstable layered structures and sluggish reaction kinetics limit their further development. To overcome these limitations, metal ions (Na+ and Zn2+) are pre-intercalated into ammonium vanadate to modify the interlayer spacing and enhance charge transfer kinetics. Additionally, the impact of different pre-intercalated ions on the structure and properties of ammonium vanadate is systematically investigated. Furthermore, we successfully synthesized ammonium vanadate cathode materials (Na0.13(NH4)0.48V2O5·0.6H2O, Na0.13-NVO) featuring stable nanostructures by optimizing the pre-embedded Na+ content. In this case, pre-intercalated sodium ions could expand the layer spacing of ammonium vanadate (9.14 Å), reduce the electrostatic interaction of Zn2+ with the V–O framework, and boost the Zn2+ diffusion rate. Benefitting from these strengths, the Na0.13-NVO electrode exhibits a specific capacity of 365.4 mAh g–1 at 0.5 A g–1, along with a good cycling stability of 98.1% capacity retention over 2000 cycles at 5 A g–1. This work supplies further insights into designing ammonium vanadate with pre-embedded metal ions and aids the development of high-performance AZIB cathodes.