In this study, long carbon nanofibers (CNFs) were grown on graphene nanoplatelets (GNPs) by chemical vapor deposition (CVD) technique to develop three-dimensional (3D) bicomponent nanostructures. The structure and properties of graphene before and after CVD process were investigated in details. X-ray photoelectron analysis depicted the formation of Fe-C bonds by the deposition of carbon atoms on the catalyst surface of Fe2O3. This hybrid additive was firstly used as a reinforcing agent in melt compounding to fabricate PA6.6-based nanocomposites with enhanced mechanical and thermal properties. Both GNP and CNF-GNP have enough surface oxygen functional groups to improve the interfacial interactions with polyamide matrix and thus provide good wettability. Also, both neat GNP and its bicomponent additive with CNF also acted as a nucleating agent and allowed the crystal growth in nanocomposite structure. Homogeneous dispersion of nanoparticles was achieved by using thermokinetic mixer during compounding by applying high shear rates. Mechanical results showed that 23 and 34% improvement in flexural and tensile modulus values, respectively, was attained by the addition of 0.5 wt % CNF-GNP hybrid additive. The heat distortion temperature and Vicat softening temperature of the resulting PA6.6 nanocomposites were improved compared to neat PA6.6 material indicating performance enhancement at higher service temperature conditions. CNF was successfully grown on Fe-loaded GNP by CVD method and this hybrid additive was compounded with PA6.6 by melt-mixing process. Mechanical results showed that 34% improvement in tensile modulus value was attained by the addition of 0.5 wt % CNF-GNP hybrid additive because it acted as a nucleating agent and allowed the crystal growth in the nanocomposite structure. (c) 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48347.