Polyvinylidene difluoride (PVDF) and its copolymers are commonly used in triboelectric nanogenerators (TENGs) due to their flexibility and good mechanical–electrical properties. In this study, poly[(vinylidene fluoride)-co-trifluoroethylene] [P(VDF-TrFE)] composites were fabricated by embedding polydopamine (PDA)-coated cobalt ferrite nanorods (RCFO). A stripe-like microstructure was formed by applying a magnetic field during the curing process. The TENG was built with a polytetrafluoroethylene (PTFE) film as the negative friction material. Due to the enhanced micro–nano structure of the P(VDF-TrFE) films, the increased charge transfer occurred between the RCFO@PDA/P(VDF-TrFE) composite film and the PTFE film. Good triboelectric performance was realized, with an open-circuit voltage of 33.20   V, a short-circuit current of 1.20 μA, and a transferred charge of 13.17 nC at a frequency of 5   Hz and a vertical contact force of 15   N. Additionally, a peak power density of 32.5 μW cm −2 was achieved when connected to an external load resistor of 20 MΩ. In practical applications, the TENG could directly illuminate a series of 36 connected light-emitting diodes without the need for capacitors. The device's ability to capture stray magnetic fields was also demonstrated. A wireless transmission-based remote security system was demonstrated as the self-powered sensor in a noncontact mode.