Large-scale preparation of cheap and high-performance carbonaceous materials is in urgent need due tothe huge demand of carbonaceous materials-organic binder composites for Joule heating. Here, carbonbasedelectrothermal composites with high electrical conductivity were fabricated by adjusting the morphologyand structure of pitch-based carbonaceous materials (PC) through the use of graphene asstructure-directing agent to tune the orientation and carbonization of coal pitch. It is demonstrated thatthe addition of graphene can effectively promote the formation of graphitized carbon, increase the contentof sp2C, reduce defective carbon and increase the graphite interlayer spacing. 1% graphene-added PCPVDFcomposite exhibits 290% increase in the carrier concentration, 190% enhancement in mobility, and67% reduction in the volume resistivity compared to PC-PVDF composite. Molecular simulations elucidatethat the graphene edges favor pitch carbonization and improve the orientation factor and energy gap ofcarbon materials. This study provides clues for design of low-cost pitch-derived carbon materials-bindercomposites.