The reportedly synergistic effects of carbon nanotubes (CNTs) and graphene hybrids have prompted strong demand for an efficient modifier to enhance their dispersion. Here, we investigated the ability of poly(acrylonitrile) (PAN) to overcome the van der Waals interaction of multi-walled CNTs (MWCNTs) and graphene by employing a simple wrapping process involving ultrasonication and subsequent centrifugation of PAN/MWCNT/graphene solutions. The physical wrapping of MWCNTs and graphene with PAN was investigated for various PAN concentrations, in an attempt to simplify and improve the polymer-wrapping process. Transmission electron microscopy analysis confirmed the wrapping of the MWCNTs and graphene with PAN layers. The interaction between the graphitic structure and the PAN molecules was examined using proton nuclear magnetic resonance, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and Raman spectroscopy. The obtained results revealed that the cyano groups of the PAN molecules facilitated adhesion of the PAN molecules to the MWCNTs and graphene for polymer wrapping. The resulting enhanced dispersion of MWCNTs and graphene was verified from zeta potential and shelf-life measurements.