Triboelectric nanogenerators (TENGs) are a new, low-cost, and easy-to-manufacture technology for converting mechanical energy into electrical energy. TENGs have great potential to be used in electronic devices, but their energy efficiency is low for use in commercial products today. The most important way to increase the energy efficiency of TENGs is to develop tribo-positive and tribo-negative materials with a large surface area and high dielectric coefficients. Herein, cetrimonium bromide (CTAB) and dodecyl trimethyl ammonium bromide (DTAB) organic molecule-doped polyvinylpyrrolidone (PVP) nanofibers are tested as a positive dielectric layer against the negative dielectric layer made of polyacrylonitrile (PAN) nanofiber. The results reveal that CTAB and DTAB additives of 1, 2.5, and 5 wt% increase the tribo-potential of PVP, while the additives of 7.5 and 10 wt% decrease the tribo-potential of PVP. According to the electrical measurements, the maximum open-circuit voltages are obtained as 500 and 515 V, whereas the maximum powers were obtained as 25.02 and 26.52 mW for the TENGs made of 5 wt% CTAB- and DTAB-doped PVP nanofibers, respectively. The proposed cationic surfactant-doped nanofibers can be employed as a positive dielectric layer to increase the energy efficiency and power density of TENGs.