AbstractA novel composite material Na2V6O16·3H2O‐AlxV2O5 (NVO‐AVO) is designed and synthesized for the first time in aqueous zinc ion battery cathode. The electrochemical behavior is elucidated in detail using in situ and ex situ techniques. The NVO‐AVO is simple, inexpensive, and safe to fabricate and contributes to the synergistic effect of orthorhombic AlxV2O5 (AVO) and monoclinic Na2V6O16·3H2O (NVO), the NVO‐AVO composites have fast Zn2+ kinetics and exhibit good electrochemical properties. At 300 mA g−1, the specific capacity is as high as 392.5 mA h g−1, and even more excitingly, NVO‐AVO remains a specific capacity of 160.6 mA h g−1 even after 18 300 cycles at 5000 mA g−1, which is significantly better than the stability of both NVO and AVO. The distinctive V3O8 layered structure in Na2V6O16·3H2O facilitates the diffusion of Zn2+, and structural water located between the V3O8 layers facilitates rapid charge transfer by widening the gallery spacing and supposing more storage sites for Zn2+. In addition, AlxV2O5 forms [AlO6] octahedral units that enhance structural stability and play a crucial role in maintaining long‐term cycling stability. This work supports the theoretical basis and technical support for the development and extension studies of new vanadium‐based electrode materials.