Triboelectric nanogenerator (TENG) technology is one of the new, low-cost, and simple methods used to convert mechanical energy into electrical energy. Despite having so many advantages, the energy efficiency of this technology is extremely low. Therefore, their current performance needs to be improved so that they can be used more in daily life. Nanofibers (NFs) are one of the most important material groups that can be used for this technology due to their large surface area–volume ratio, easy production, low cost, and simplicity. Herein, Nylon 6.6 and polyacrylonitrile are used as tribopositive and tribonegative dielectric layers, respectively. To increase the output performances of the TENG system, different weight ratios (1, 2, 3 wt%) of phthalocyanine containing zinc-based carborane units (ZnPc) are added into the Nylon 6.6 NFs. In accordance with the obtained results, the maximum open circuit voltage and power are measured as 228 V and 7.76 mW, respectively. These results correspond for the TENG system with 1% by weight ZnPc doped into the NFs. These results show that high-efficiency TENG systems can be obtained with nanofiber-based dielectric layers and can be used effectively in self-powered systems.