In the dynamic fields of information science and electronic technology, there is a notable trend towards leveraging carbon materials, favored for their ease of synthesis, biocompatibility, and abundance. This trend is particularly evident in the development of memristors, benefiting from the unique electronic properties of carbon to enhance device performance. This study utilizes sensitized chemical evaporation and spin-coating carbonization techniques to fabricate nickel-cobalt coated carbon composite nanofibers (SC-NCMNTs). Novel polyimide (PI) matrix composite memory devices were fabricated using in situ polymerization technology. Transmission electron microscopy (TEM) and micro-Raman spectroscopy analyses validated the presence of dual interface structures located between the Ni-Co-MWNTs, carbon composite nanofibers, and PI matrix, revealing a significant number of defects within the SC-NCMNTs/PI composite films. Consequently, this results in a tunable charge trap-based ternary resistive switching behavior of the composite memory devices, exhibiting a high ON/OFF current ratio of 104 and a retention time of 2500 s at an operating voltage of less than 3 V. The mechanism of resistive switching is thoroughly elucidated through a comprehensive charge transport model, incorporating molecular orbital energy levels. This study provides valuable insights for the rational design and fabrication of efficient memristors characterized by multilevel resistive switching states.