Aramid (Ar), produced from the reaction of aromatic diamines and diacid chloride, was reactively compatibilized with amino-functionalized polystyrene (APS) to explore blend morphology and interfacial cohesion. Two blend systems, Ar/PS and Ar/APS, were investigated over a range of pristine polystyrene (PS) or modified APS ratios. Morphology and thermal and mechanical properties were probed to evaluate the effect of amine units of APS on the compatibility with Ar. π-π stacking interactions in tandem with the random distribution of graft attachment locations and polydispersity of graft length in Ar-g-APS copolymer, aided merger of unreacted chains to drive molecular self-assembly process thus fortifying the nanostructured blends. Considerable augmentation of the blend morphology and thermal stability was achieved by incorporation of reactivity into Ar/APS system. A 20 wt % APS-containing blend was found to demonstrate optimum mechanical reinforcement, complemented by the optimal, thermal, and morphological profiles of the same blend. Future prospects are envisaged.