The inherent trade-off between electrical conductivity (σ) and the Seebeck coefficient (S) poses a fundamental challenge for developing high-performance conductive polymer/SWCNT thermoelectric composites in wearable electronics. In this study, an innovative synergistic strategy integrating molecular engineering with a multi-level composite architecture is used, and a one-step electrochemical method is used to synthesize an aniline (ANI) and 3,4-ethylenedioxythiophene (EDOT) copolymer (P(ANI-co-EDOT)) directly on the SWCNT network. The incorporation of EDOT units into the polyaniline (PANI) chain enlarges the delocalized electron system and enhances carrier mobility, boosting the σ of the composite film to 4.0 times that of pristine SWCNT and 2.0 times that of PANI/SWCNT. This results in a remarkable σ of 2681.1 S cm-1 and a power factor (PF) of 196.0 μW m-1 K-2. Furthermore, we have achieved a synergistic enhancement of σ and S by depositing high-S tellurium (Te) nanoparticles onto high-σ P(ANI-co-EDOT)/SWCNT framework, elevating the PF to 215.1 μW m-1 K-2. A solar thermoelectric generator fabricated from this composite film produces an open-circuit voltage of 14.7 mV and an output power of 1137 nW under 2-sun illumination (2 kW m-2), demonstrating its potential for concentrated solar energy harvesting. Therefore, this work validates that electrochemically driven molecular engineering combining with a multi-level composite design is a highly effective avenue for advancing the performance of conductive polymer/SWCNT thermoelectric materials.