This work exhibits anionic sodium dodecyl sulfate (SDS), nonionic triblock copolymer F127, and polyaniline (PANI) nanostructures. The nanorod shaped PANI-SDS-F127 1:1 demonstrates noteworthy features—scalable and extended electrical characteristics, dielectric response, and significance in high-density energy storage devices. High-frequency measurements (1 MHz–1 GHz) preserve dielectric relaxation, which is attributed to excellent charge polarization. Uniformly distributed PANI nanorods align with the induced electric field and develop high current density (J ∼ 5.270 × 105 mA m–2), electric displacement (Dmax ∼ 7.408 × 105 C m–2), and lower impedance (Zs ∼ 3.28 Ω), which result in an improved charge polarization leading to increased capacitance (Cs ∼ 6.21 μF). These properties yield notable energy density (Ue ∼ 1.08 J cm–3) and signify a polymer matrix viable to high-density energy storage capacitor devices that would be actively favorable in developing efficient electronic and electrical devices.