Exfoliated graphite (ExG) embedded in a polymeric matrix represents an accessible, cost-effective, and sustainable method for generating nanosized graphite-based polymer composites with multifunctional properties. This review article analyzes diverse methods currently used to exfoliate graphite into graphite nanoplatelets, few-layer graphene, and polymer-assisted graphene. It also explores engineered methods for small-scale pilot production of polymer nanocomposites. It highlights the chemistry involved during the graphite intercalation and exfoliation process, particularly emphasizing the interfacial interactions related to steric repulsion forces, van der Waals forces, hydrogen bonds, pi-pi stacking, and covalent bonds. These interactions promote the dispersion and stabilization of the graphite derivative structures in polymeric matrices. Finally, it compares the enhanced properties of nanocomposites, such as increased thermal and electrical conductivity and electromagnetic interference (EMI) shielding applications, with those of neat polymer materials.