The current study focuses on the influence of low nano-carbon loading (<0.5 wt%) to influence the structural development in the nano-composite fiber. Post fiber-spinning procedures including hot-stage drawing and annealing are used to induce ordered polymer domains assisted by the nano-carbon in the materials. The subsequent fibers exhibit stiffness and toughness well above the theoretically predictions. It was found that drawing and annealing procedures significantly enhanced the dimensions of fibrils, sub-fibrillar lamellar, and sub-lamellar grain size for the nano-composites as compared to control samples. This work discusses the role of the nano-filler toward the structural evolution of the polymer matrix during processing. The relationships between processing approaches and subsequent properties also provide new perspective for the use of nano-carbon as spinning aides to facilitate polymer ordering. It also brings to light the potential for producing high-performance composite materials from flexible polymers by minimal inclusion of carbon nano-fillers, which is attractive for commercial production in terms of cost.