In efforts to characterize and understand the properties and processing of phenylethynyl-terminated imide (LaRC PETI-5, simply referred to as PETI-5) oligomers and polymers as a high-temperature sizing material for carbon fiber-reinforced polymer matrix composites, PETI-5 imidization and thermal curing behaviors have been extensively investigated based on the phenylethynyl end-group reaction. These studies are reviewed here. In addition, the use of PETI-5 to enhance interfacial adhesion between carbon fibers and a bismaleimide (BMI) matrix, as well as the dynamic mechanical properties of carbon/BMI composites, are discussed. Reports on the thermal expansion behavior of intercalated graphite flake, and the effects of exfoliated graphite nanoplatelets (xGnP) on the properties of PETI-5 matrix composites are also reviewed. The dynamic mechanical and thermal properties and the electrical resistivity of xGnP/PETI-5 composites are characterized. The effect of liquid rubber amine-terminated poly(butadiene-co-acrylonitrile) (ATBN)-coated xGnP particles incorporated into epoxy resin on the toughness of xGnP/epoxy composites is examined in terms of its impact on Izod strength. This paper provides an extensive overview from fundamental studies on PETI-5 and xGnP, as well as applied studies on relevant composite materials.