In recent years, the thermoelectric properties of one-dimensional boron nitride nanomaterials have gradually attracted widespread attention of researchers in the world. In this paper, boron carbon nitrogen based composite nanofiber films were prepared by electrospinning. It is found that the diameter of nanofibers decreases in BCNNTs/PVA/PEDOT composite films when electrospinning voltage rises, while diameter increases as PVA and BCNNTs concentration increase of electrospinning precursor solution. Finally, thermoelectric power factor is investigated of the composite nanofiber films. It is verified that thermoelectric properties of the films closely related to electrospinning quality. However, fiber density of single-layer BCNNTs/PVA/ PEDOT nanofiber film is too low, folding increase the density and thickness of multilayer BCNNTs/PVA/PEDOT nanocomposite fiber films, and the thermoelectric characteristics are significantly improved. The Seebeck coefficient can reach 3.62 mV/K and the power factor is 29.09 nW/mK 2 .