Carbon nanofibers (CNF) exhibit special morphological features pertaining to their high aspect ratio. This work explores the polyelectrolyte (PDDA, Poly (diallyl dimethylammonium) chloride) wrapping on CNF and the interaction mechanism between them in the presence of a surfactant (octyl-phenol-ethoxylate (Triton X-100)). The wrapping has been achieved via a simple on/off ultrasonication methodology. PDDA behaves as a dispersing agent and an electron acceptor; the inter-molecular charge transfer takes place between CNF (electron donor) and PDDA, Triton X-100 works as a dispersing agent too but it affects pronouncedly the inter-molecular charge transfer. It has been observed that pi-pi, hydrophobic-hydrophilic, weak electrostatic, and van der Waals interactions all sum up to supramolecular interactions in CNF + PDDA + Triton X-100; leading to an augmented N content as compared to carbon nanotubes or graphene in a similar system. This system could work as the metal-free electrocatalyst for the oxygen reduction reaction in a Fuel cell. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.