Polymer composite materials fabricated from acrylonitrile-derived polymers (such as polyacrylonitrile, nitrile butadiene rubber, styrene-acrylonitrile, acrylonitrile butadiene styrene) with suitable fillers have found tremendous applications due to their highly desirable properties. Graphene, a versatile 2D carbon nanomaterial, with extraordinary properties has been adopted as an effective filler component of a wide range of acrylonitrile-based polymer composites. The modified and functionalized graphene-based nanomaterials were incorporated into the acrylonitrile-based polymer matrix to enhance their various properties. In contrast to conventional 1D carbon nanoparticles, the incorporation of this graphene into the polymer matrix resulted excellent improvement in mechanical, electrical, rheological, and thermal, as well as frictional properties. This has offered advances in diverse applications such as sensors, flexible electronics, Li-S battery, damping, structural, microwave shielding, aircraft, spacecraft, automobile, and so forth. Particularly, the excellent EMI (Electromagnetic interference) shielding ability of these acrylonitrilebased polymer/graphene composites has been explored widely in microelectronics. This review focuses on the recent progress and new strategies in the development of different acrylonitrile-based polymer/graphene nanocomposites.