Nanoscale surface architecturing of high-performance organic fibers offers a viable avenue for enhancing interfacial adhesion and imparting additional functionality to fiber-reinforced polymer composites. Herein, the Micro-Swelling-Induced Nanoscale Hydrogen-Bond Network (MiNaHN) strategy is introduced, which integrates a robust nano-interface with the aramid backbone while preserving fiber integrity. The mild solvent-assisted micro-swelling treatment locally unlocks intermolecular hydrogen bonds, revealing amide sites that guide multivalent hydrogen-bonded self-assembly of 3-amino-1,2,4-triazole-functionalized reduced graphene oxide. Concomitantly, aramid nanofibers dispersed in phenolic matrix establish complementary bonding with both the resin and the modified fibers. The resulting architecture forms a continuous and dynamic hydrogen-bond network that bridges the fiber–matrix interface and the surrounding matrix. This integrated nano-interface raises the tensile strength of aramid/polytetrafluoroethylene fabric composites by 71.9%, while lowering the wear volume and friction coefficient by 45.4% and 31.5%, respectively. Microscopic and spectroscopic analyses show that the nanostructure promotes durable tribofilm formation and efficient stress dissipation without compromising the intrinsic properties of fibers. The MiNaHN strategy delivers a scalable route for activating chemically inert organic fibers through molecularly connected nano-interfaces and is broadly applicable to composite systems that require simultaneous gains in mechanical robustness and tribological stability.