A method for forming a nanofiber adhesive structure includes, in one embodiment, providing a plurality of generally parallel fiber bundles secured in a first binder and in which each of the fiber bundles includes a plurality of generally parallel fibers secured in a second binder. The fibers have a diameter between about 200 nanometers to about 400 nanometers. A portion of the first binder is dissolved from the structure to expose end portions of the plurality of fiber bundles having a length of about 100 microns. A portion of the second binder of the exposed end portions of the plurality of fiber bundle is dissolved to expose the fibers having a length of about 15 microns. Thin slices may be made and assembled on a web to provide a gecko tape having adhesive properties based on Van der Waals forces.