The micro- and nano-scale fibrillar structures found on the feet of spiders and geckos function as adhesion devices which allow them to adhere to both molecularly smooth and rough surfaces. This adhesion has been argued to arise from intermolecular forces, such as van der Waals (vdW) force, acting at the interface between any two materials in contact. Thus, it is possible to mimic their adhesion using synthetic nanostructured analogs. Herein, we report the first successful pull-off force measurements on a single electrospun fiber and show the potential of using electrospinning to fabricate adhesive analogs. A single fiber is glued to the atomic force microscope cantilever, and its adhesion to a metal substrate is studied by recording the pull-off force/displacement curves. The measured adhesive force of 18 nN matches closely that of their biological counterparts. Similar to natural structures, the adhesive mechanism of these electrospun structures is controlled by vdW interactions.