Ionic liquids (ILs) with long alkyl substituted groups, including 1-docosanyl-3-methylimidazolium bromide (IL-1) and 1-docosanyl-3-methylimidazolium hexafluorophosphate (IL-2), were synthesized and used to modify the surface of carbon nanofibers (CNF). The nanocomposite film prepared by solution-blending of ionic liquid modified CNF (i-CNF) and ultrahigh molecular weight polyethylene (UHMWPE) displayed better toughness when compared with pure UHMWPE even at very low concentrations (e.g. 0.4 wt%). The effect of ionic liquids on the elongation-to-break ratio of this nanocomposite system was investigated. The ionic liquid with hexafluorophosphate as the anion was more efficient to increase the toughness of UHMWPE due to the improved compatibility of IL with UHMWPE in the polymer matrix than that of the bromide. The rheological behavior of molten nanocomposites revealed that the storage modulus and the complex viscosity decreased with increasing ionic liquid content in the high frequency region. However, a reverse trend was observed when the frequency was less than 0.05 s(-1). In-situ monitoring in the change of crystallinity of the nanocomposite during tensile deformation suggested a mechanism of sliding between UHMWPE crystal regions and the surface of carbon nanofibers. (C) 2013 Elsevier Ltd. All rights reserved.