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Triblock copolymer of poly(p-dioxanone) and polyethylene glycol end-capped with pyrene moieties((Py-PPDO)_2-b-PEG) was synthesized and used as modifier for multi-wall carbon nanotubes(MWCNTs).Nano-aggregates((Py-PPDO)_2-b-PEG@MWCNTs) with shish-kebab like partially wrapped morphology and very good stability were obtained by incorporating the copolymer with MWCNTs.The bare MWCNT sections of(Py-PPDO)_2-b-PEG@MWCNTs were able to induce n-n interactions with graphene(GE) and resulted in a novel GE/(Py-PPDO)_2-b-PEG@MWCNTs hybrid.The dispersity of GE in solution or polymer matrix was therefore greatly improved.The PCL nanocomposite films using GE/(Py-PPDO)_2-bPEG@MWCNTs as hybrid nanofiller exhibited obviously improved mechanical properties especially at very low hybrid nanofiller content.The influence of the nanofiller content and feed ratio of GE/MWCNTs on the mechanical properties of composites films was evaluated.When the feed ratio of GE to MWCNTs is 2:8 and the total loading of nanofiller is only 0.01 wt%,the tensile strength of the composite film increased by 163%and the elongation at break increased by 17% compared to those of neat PCL These results can be attributed to fine dispersion of the nanofillers in PCL matrix and the hybrid interactions between GE and MWCNTs.Therefore,this work provides a novel method for preparing polymer nanocomposites with high mechanical performance and low nanofiller loading.