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As a remarkable multifunctional material, ferroferric oxide (Fe₃O₄) exhibits considerable potential for applications in many fields, such as energy storage and conversion technologies. However, the poor electronic and ionic conductivities of classical Fe₃O₄ restricts its application. To address this challenge, Fe₃O₄ nanoparticles are combined with graphene oxide (GO) via a typical hydrothermal method, followed by a conductive wrapping using poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic sulfonate) (PEDOT:PSS) for the fabrication of composite films. Upon acid treatment, a highly conductive porous Fe₃O₄@RGO/PEDOT:PSS hybrid is successfully constructed, and each component exerts its action that effectively facilitates the electron transfer and subsequent performance improvement. Specifically, the Fe₃O₄@RGO/PEDOT:PSS porous film achieves a high specific capacitance of 244.7 F g⁻¹ at a current of 1 A g⁻¹. Furthermore, due to the facial fabrication of the highly conductive networks, the free-standing film exhibits potential advantages in flexible thermoelectric (TE) materials. Notably, such a hybrid film shows a high electric conductivity (σ) of 507.56 S cm⁻¹, a three times greater value than the Fe₃O₄@RGO component, and achieves an optimized Seebeck coefficient (S) of 13.29 μV K⁻¹ at room temperature. This work provides a novel route for the synthesis of Fe₃O₄@RGO/PEDOT:PSS multifunctional films that possess promising applications in energy storage and conversion.