The rapid development of TE generators for harvesting energy from the human body has made new demand on its TE performance and wearability. In this context, electrospinning and in situ synthesis process are employed to fabricate Ag NPs coated PEDOT:PSS/PVA flexible self-supporting nanofiber film. The introduction of Ag NPs not only creates a great quantity of organic-inorganic interfaces which make an increase both in charge transfer channels and phonon scattering, but also greatly improve the mechanical properties of nanofiber film. As a result, the electrical conductivity has been greatly improved without losing too much Seebeck coefficient of the composite film, a maximum power factor up to 1.2 mu W m(-1 )K(-2 )at room temperature is achieved. A flexible TE generator consisting of 5 strips is designed using the as-prepared composite film and can produce an output voltage of 3.43 mV at a 30.1 K temperature difference.