This study investigated the electrospinning of polystyrene solutions using added unmodified and modified (with grafted nitrobenzene and trifluoromethyl benzene functionalities and polystyrene brushes) cellulose nanocrystals (CNCs). A strong correlation existed between the formation of beads on the fibers and the degree of dispersion of CNC particles in the electrospinning mixtures. Agglomerates of CNC particles always concentrated in the form of beads. The best dispersion in N,N dimethylformamide (DMF) mixtures was obtained using CNC-2 surfaces that were modified using trifluoromethyl benzene functional groups. Using CNC-2 also resulted in both uniform and bead-free electrospun fibers. Despite good dispersion in DMF, the use of grafted polystyrene (PS) chains with CNC-g resulted in beads above a 1.0% concentration level. This result is attributed to more favorable interactions between the CNC-g brushes during the DMF solvent evaporation stage of electrospinning. The electrospinning of CNC/PS nanocomposites at very low CNC concentrations (<1.0%) showed strong adhesion bonds at the polymer-CNC interfaces. Excellent mechanical properties were also produced by using interpenetrating networks of surface brushes. (C) 2018 Elsevier Inc. All rights reserved.