K-ion batteries (KIBs) are promising for large-scale electrical energy storage owing to the abundant resources and the electrochemical specificity of potassium. Among the positive electrode materials for KIBs, vanadium-based polyanionic materials are interesting because of their high working voltage and good structural stability which dictates the cycle life. In this study, a potassium vanadium oxide phosphate, K6(VO)2(V2O3)2(PO4)4(P2O7), has been investigated as a 4 V class positive electrode material for non-aqueous KIBs. The material is synthesized through pyrolysis of a single metal-organic molecular precursor, K2[(VOHPO4)2(C2O4)] at 500 °C in air. The material demonstrates a reversible extraction/insertion of 2.7 mol of potassium from/into the structure at a discharge voltage of ∼4.03 V vs. K. Operando and ex situ powder X-ray diffraction analyses reveal that the material undergoes reversible K extraction/insertion during charge/discharge via a two-phase reaction mechanism. Despite the extraction/insertion of large potassium ions, the material demonstrates an insignificant volume change of ∼1.2% during charge/discharge resulting in excellent cycling stability without capacity degradation over 100 cycles in a highly concentrated electrolyte cell. Robustness of the polyanionic framework is proved from identical XRD patterns of the pristine and cycled electrodes (after 100 cycles).