This work explores the development of a triboelectric nanogenerator (TENG) based on polyacrylonitrile (PAN) and molybdenum disulfide (MoS2) nanosheets composite fibers for enhancing tribo‐positive electricity to power backscatter communication systems, contributing to the sustainable internet of things (IoT) nodes in future 6 G networks. By incorporating different concentrations of MoS2 (1, 2, 3, and 4 wt%) nanosheets into PAN nanofibers via electrospinning, the nanocomposite fiber‐based TENGs exhibit improved triboelectric properties. The TENG based on PAN/4% MoS2 nanocomposite fiber mat achieve a peak open‐circuit voltage of 296 V and a short‐circuit current of 6.16 μA, which represents an ≈95% and 77% enhancement, respectively, in comparison with the TENGs based on neat PAN nanofiber mat. The enhanced charge transfer ability at the PAN and MoS2 nanosheet interface, the increased dielectric properties, the rougher surface morphology of the composite nanofibers contribute to the enhancements in triboelectric performance. These TENGs are integrated with the backscatter communication system to power a wireless identification and sensing platform (WISP) tag, demonstrating extended transmission range and improved real‐time data acquisition. These findings suggest that TENGs can play a significant role in sustainable energy solutions for 6 G‐enabled IoT applications.