Potassium-ion batteries (KIBs) represent a promising energy storage solution owing to the abundance of potassium resources. The efficacy of KIBs relies significantly on the electrochemical attributes of both their electrode materials and electrolyte. In the current investigation, we synthesized a layered compound K2[(VOHPO4)2(C2O4)]·2H2O via a heterogeneous nucleation approach and assessed its viability as a cathode material for KIBs. When integrated with a salt-concentrated electrolyte with oxidation stability over 6 V, the compounds exhibits a high discharge potential of 4.1 V (vs. K+/K) alongside a reversible capacity of 106.2 mAh g−1. Furthermore, there is no capacity decay after 500 cycles at 100 mA g−1. This study shows the promise of layered metal organic frameworks as high-potential materials for KIBs.