Herein, poly­(3,4-ethylenedioxythiophene):poly­(styrenesulfonate) (PEDOT:PSS) coated Cu x Se y (PC-Cu x Se y ) nanowires are prepared by a wet-chemical method, and PEDOT:PSS/Cu x Se y nanocomposite films on flexible nylon membrane are fabricated by vacuum assisted filtration and then cold-pressing. XRD analysis reveals that the Cu x Se y with different compositions can be obtained by adjusting the nominal Cu/Se molar ratios of their sources. For the composite film starting from a Cu/Se nominal molar ratio of 3, an optimized power factor of ∼270.3 μW/mK2 is obtained at 300 K. Moreover, the film exhibits a superior flexibility with 85% of the original power factor retention after bending for 1000 cycles around a rod with a diameter of 5 mm. TEM and STEM observations of the focused ion beam (FIB) prepared sample reveal that it is mainly attributed to a synergetic effect of the nylon membrane and the composite film with nanoporous structure formed by the intertwined nanowires, besides the intrinsic flexibility of nylon. Finally, a thermoelectric prototype composed of nine legs of the optimized hybrid film generates a voltage and a maximum power of 15 mV and 320 nW, respectively, at a temperature gradient of 30 K. This work offers an effective approach for high TE performance inorganic/polymer composite film for flexible TE devices.