We report the fabrication of hierarchical poly(vinylidene fluoride) (PVDF) fibrous structures using a unique fabrication technique based on electrospinning. Electrospinning was used to fabricate aligned PVDF fibrous membranes. These membranes were then brought in contact with anodized aluminum oxide (AAO) template and then heat-treated above the glass transition temperature (T (g)) of the polymer to assist the flow of polymer within the cylindrical pores of AAO template. Scanning electron microscopy images confirmed that this approach lead to the growth of nanopillars on the surface of PVDF fibers. Nanoindenter was used to measure the pull-off force that was required to completely detach the indenter from the samples. To investigate the effect of hierarchy, pull-off force required to detach the indenter from neat PVDF fibers was determined and compared with the pull-off force recorded for hierarchical fibers. The effect of indentation depth was also investigated on both PVDF fibers and PVDF fiber with nanopillars. Significant pull-off force recorded indicates that these PVDF hierarchical fibrous structures can be potentially used for dry-adhesive applications.