Abstract: To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials (LiNi_0.8Co_0.15Al_0.05O₂, NCA), lithium lanthanum titanate (LLTO) nanofiber and carbon-coated LLTO fiber (LLTO@C) materials were introduced to polyvinylidene difluoride in a cathode. The enhancement of the conductivity was indicated by the suppressed impedance and polarization. At 1 and 5 C, the cathodes with coupling conductive paths had a more stable cycling performance. The coupling mechanism was analyzed based on the chemical state and structure evolution of NCA after cycling for 200 cycles at 5 C. In the pristine cathode, the propagation of lattice damaged regions, which consist of high-density edge-dislocation walls, destroyed the bulk integrity of NCA. In addition, the formation of a rock-salt phase on the surface of NCA caused a capacity loss. In contrast, in the LLTO@C modified cathode, although the formation of dislocation-driven atomic lattice broken regions and cation mixing occurred, they were limited to a scale of several atoms, which retarded the generation of the rock-salt phase and resulted in a pre-eminent capacity retention. Only NiO phase “pitting” occurred. A mechanism based on the synergistic transport of Li ions and electrons was proposed.