β-Bi₂O₃-Bi₂O₂CO₃ dispersed polypyrrole (PPy/β-Bi₂O₃-Bi₂O₂CO₃) composite is electrochemically deposited on stainless steel mesh (SSM) surface in an acetonitrile solution of pyrrole monomer and pre-synthesized β-Bi₂O₃-Bi₂O₂CO₃ nanoparticles. The coating is characterized compared with those of the PPy homopolymer coating and β-Bi₂O₃-Bi₂O₂CO₃ powder using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), XPS, XRD, TEM, and FESEM. Flower-shaped spherical nanoparticles containing β-Bi₂O₃-Bi₂O₂CO₃ phases are encapsulated in the partially oxidized PPy clusters composed of small nanospheres, thus dispersed well in the composite. The PPy/β-Bi₂O₃-Bi₂O₂CO₃ coating exhibits a more capacitive behaviour than the PPy coating due to the electro-generation of Bi⁵⁺ in the β-Bi₂O₃-Bi₂O₂CO₃ phases during the synthesis of composite and the supercapacitor cycling. The coated electrode provides a higher pseudocapacitive contribution (67.4 %) thanks to the mixed metal oxide of β-Bi₂O₃-Bi₂O₂CO₃ in addition to PPy, exhibited a specific capacitance of 360 F g⁻¹ in 100 mM Li₂SO₄. Bi₂O₂CO₃ with a layered structure contributes to enlarge of active surface area, conductivity, and catalytic performance. A solid-state asymmetric cell is fabricated with polyvinyl alcohol (PVA)/Li₂SO₄ using 10 mg cm⁻² mass-loaded PPy/β-Bi₂O₃-Bi₂O₂CO₃ composite- and polyvinyl chloride (PVC)/carbon- coated SSM electrodes. The device provides 64.2 Wh kg⁻¹ specific energy and 350 W kg⁻¹ specific power at 0.5 A g⁻¹ with a coulombic efficiency of 90 % and high stability of about 97 % for 5000 cycles. The electrode has the potential to be used as a binder-free electrode in high-performance supercapacitors.