<p>Conventionally synthesized polypyrrole (PPy-s) via solution polymerization exhibits randomly aligned molecular chains and low crystallinity, which limits its specific energy and long-term cycling stability. In this work, we systematically optimized the interfacial polymerization of pyrrole, resulting in polypyrrole (PPy-i) with a flake-like structure, high crystallinity, enhanced electrical conductivity, and improved stability due to ordered molecular stacking. As expected, PPy-i demonstrates a specific capacitance of 220 F g⁻¹ at 1 A g⁻¹, three times higher than that of PPy-s (69 F g⁻¹). A zinc hybrid supercapacitor (ZHSC) based on PPy-i achieves a capacitance of 491 F g⁻¹ at 10&#xa0;mV&#xa0;s⁻¹, along with a stable charge storage capacitance of 352 F g⁻¹ at 0.5 A g⁻¹, and retains 94% of its initial capacitance after 10,000 cycles. Notably, the PPy-i cathode endows the ZHSC with a high specific energy of 115 Wh kg⁻¹ at 696 W kg⁻¹, outperforming most PPy-based electrodes. In summary, interfacial polymerization offers an effective strategy for tailoring the microstructure of polypyrrole and enhancing its electrochemical performance.</p>