A new type of platelet-like ammonium vanadium bronze (NH4)2V6O16 is first used as cathode material for Na-ion battery. The discharge capacity and cycling stability is improved by the intercalation of Na+ and using NaPF6 as electrolyte. Raman spectrum shows that the crystalline structure of (NH4)2V6O16 is changed after the intercalation of Na+ to (NH4)2V6O16. Furthermore, the obtained sodium ammonium vanadium bronze shows smaller charge transfer resistance than (NH4)2V6O16, which would favor superior discharge capacity and good cycling stability. Additionally, NaPF6 is prior to NaClO4 as electrolyte for ammonium vanadium bronze cathode materials.