The performance limits of conventional super engineering plastics with inorganic nanofillers are surpassed by all-organic nanocomposites prepared via in situ SNAr polymerization of polysulfone (PSU) in the presence of a highly dispersed aramid nanofiber (ANF) solution. The latter is directly used, bypassing the energy-consuming, nanostructure-damaging workup process. Using only a 0.15 wt % nanofiller, the all-organic nanocomposite shows an ultimate tensile strength 1.6x higher and 3.4X tougher than neat PSU and its blending counterpart due to the mutually interactive filler and maximally homogenized matrix. The exceptional toughness of the ANF/PSU nanocomposite originates from the grafted PSU on the surface of ANF; it drives stress-delocalized deformation, as revealed by stress-absorbable viscoelastic behavior and ductile elongation of materials. This material is a promising candidate for use as a filler-interactive, high-performance nanocomposite.