Abstract: In order to make full use of the structure of the rich porous structure of metal-organic frame material (MOF) and the unique doping structure of conductive polymers, the influence of dopants on the structure and electrochemical properties of MOF/conductive polymer complexes are studied to achieve stable chemical doping. 3D flower-like ZIF-67 (Z8) was firstly prepared by controlling the ratio of Co²⁺ and 2-methylimidazole at room temperature. 5-Sulfosalicylic acid (5-SSA) doped polypyrrole (PPy)/Z8 composites were synthesized via facile in-situ polymerization. The introduction of Z8 can reduce the agglomeration of the obtained PPy microspheres. The stable chemical doping can be achieved by the multiple bonds and the conjugation effects between 5-SSA and Z8. This will be helpful for the fast transfer of electrons and electrolyte ions and the strong support for the PPy chains. The resulted composites with 10wt% Z8 loading (PPy/10wt%Z8) achieves the highest specific capacitance of 300 F·g⁻¹ among the PPy/Z8. The asymmetric supercapacitor assembled by PPy/10wt%Z8 and active carbon on carbon cloth as flexible electrodes demonstrates high areal capacitance (200 mF·cm⁻²), high energy density (71 μW·h·cm⁻²) and power density (800 μW·cm⁻²). Moreover, the flexible supercapacitor provides excellent cycle stability after 10000 cycles (80.2% capacitance retention), indicating good supercapacitive performances.