The preparation of polymer-functionalized graphene nanoribbons (PF-GNRs) in a one-pot synthesis is described. Multiwalled carbon nanotubes (MWCNTs) were intercalated by potassium under vapor- or liquid-phase conditions, followed by the addition of vinyl or epoxide monomers, resulting in PF-GNRs. Scanning electron microscopy, thermogravimetric mass spectrometry, and X-ray photoelectron spectroscopy were used to characterize the PF-GNRs. Also explored here is the correlation between the splitting of MWCNTs, the intrinsic properties of the intercalants and the degree of defects and graphitization of the starting MWCNTs. The PF-GNRs could have applications in conductive composites, transparent electrodes, heat circuits, and supercapacitors.