<p>The development of xerogel-based electrodes represents a key strategy for enhancing the electrochemical performance of supercapacitor devices. In this work, working electrodes were fabricated by depositing xerogels of hollow polyacrylic acid (HPAA) and hollow polyacrylamide (HPAM), doped with reduced graphene oxide (rGO), onto nickel foam (NF). This was achieved using a simple, low-cost electrochemical-assisted physical mixing technique, enabling efficient material integration and improved electrode performance. The synthesized HPAA/rGO and HPAM/rGO xerogel composites were systematically analyzed using Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) to confirm their structural and morphological properties. A comparative investigation between HPAA/rGO and HPAM/rGO composite electrodes on NF revealed the superiority of HPAM/rGO xerogel composite as a uniform, porous, and exfoliated architecture, which is essential for efficient electrochemical performance. Remarkably, the HPAM/rGO-based supercapacitor demonstrated an impressive specific capacitance of 1674 F g⁻¹, higher than that of HPAA/rGO 970 F g⁻¹ and excellent cycling stability, retaining approximately 82% of its capacitance after 5000 cycles at a scan rate of 5 mVs⁻¹, as validated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). This behavior is attributed to the synergistic effects of the uniformly distributed, hollow framework and the conductive rGO network, which promote rapid ion diffusion and minimize internal resistance at the electrode–electrolyte interface. Therefore, HPAM/rGO xerogel composite on NF exhibits strong potential as a next-generation, flexible, and cost-effective electrode material for energy-storage applications, particularly in supercapacitor technologies.</p>