Despite the promising potential of carbon nanotubes (CNTs) in polymer nanocomposites, their propensity for aggregation and random dispersion within the polymer matrix poses significant challenges. This study introduces a novel approach to enhance the interfacial properties between the CNTs and the polyamide 6 (PA6) matrix by anchoring the polyethyleneimine (PEI) onto the CNT surfaces. The integration of PEI, with abundant amino groups, provides the high density of nucleation sites, facilitating transcrystallization along the surfaces of the macromolecular polyethyleneimine (PEI) modified CNTs (m-CNTs). This transcrystallization process enhances the physical interactions between the m-CNTs and the PA6 matrix, resulting in the substantial improvements in the mechanical properties of the PA6 nanocomposites. Specifically, as compared to the neat PA6, the PA6/m-CNT nanocomposites exhibited the increase of 131.2 % and 54.3 % in tensile strength and Young's modulus, respectively. Additionally, the intimate contact between the embedded CNTs forms the efficient thermally conductive networks. The robust molecular interactions between the m-CNTs and the PA6 polymer chains promote the highly homogeneous dispersion within the PA6/m-CNT nanocomposites, thereby reducing the thermal resistance. This straightforward and effective method presents a viable strategy for improving the interfacial properties of the CNTs reinforced polymer nanocomposites, offering the extensive potential for the future advancements in the interfacial modifications of the polymer matrix nanocomposites.