Ionic polymer–metal composites consist of an ion-conducting polymer–gel membrane sandwiched between two flexible electrodes, representing a class of soft electroactive materials capable of large deformation under low voltage. The gel membrane, swollen with solvent, facilitates ion migration under an electric field, enabling actuation. Tailoring the interfacial architecture between the electrode and the polymer–gel membrane is pivotal for advancing high-performance IPMC actuators. This study presents a comparative investigation of three core–shell nanocomposite electrodes, fabricated via in situ polymerization, for IPMC applications. Among these, the polyaniline-coated multi-walled carbon nanotube composite exhibits a deliberately designed hierarchical structure, with a specific surface area of 32.345 m²·g⁻¹ and a conductive doped polyaniline shell, as confirmed through XPS analysis. This optimized interface enables superior charge storage and transport, endowing the corresponding electrode with a specific capacitance of 40.28 mF·cm⁻² at 100 mV·s⁻¹—3.2 times greater than that of conventional silver-based electrodes—along with a reduced sheet resistance. When integrated with a Nafion ion–gel membrane, the PANI@MWCNT electrode achieves a 67% increase in force density and a larger displacement output compared to standard devices, directly correlated with its enhanced electrical and electrochemical properties. This work highlights the critical role of core–shell interfacial engineering in governing electromechanical performance at the electrode–gel interface and offers a practical design strategy for developing high-performance, cost-effective IPMC actuators for soft robotics, flexible electronics, and related applications.