Abstract: Metal-organic frameworks (MOFs) are regarded as ideal supercapacitor electrode materials due to their high specific surface area, tunable pore structure, and abundant redox sites. However, their application in supercapacitor electrodes is limited by poor electrical conductivity and structural instability. In this study, acetic acid was used as a coordination modulator to synthesize a high-surface-area octahedral structured Zr-MOF-a via a hydrothermal method. Subsequently, through in situ oxidative polymerization, Sodium Anthraquinone-2-sulfonate (AQS) and Phosphomolybdic acid (PMA) were introduced as co-dopants to induce the ordered growth of PPy chains while constructing a 3D porous structure, thereby enhancing the electrochemical performance and cycling stability of the composite material. Electrochemical test analyses indicate that the asymmetric device assembled using the co-doped composite material ZrPPA as the cathode and activated carbon as the anode achieves a specific capacitance of 209 F·g⁻¹ at 0.5 A·g⁻¹, with an energy density of 48.9 W·h·kg⁻¹ and a power density of 350 W·kg⁻¹. At 0.5 mA·cm⁻², the areal capacitance is 305.4 mF·cm⁻², with areal energy density of 71.3 μW·h·cm⁻² and areal power density of 350 μW·cm⁻². After 10,000 cycles at a current density of 5 A·g⁻¹, the capacitance retention rate is 76.74%, demonstrating significant potential as an electrode material.