Electrodes in traditional electrospinning processes have been used to directly collect nanofibers, or to induce a modified electric field to collect aligned nanofibers. In this context, many studies have been carried out to overcome the limitations of simple metal electrodes. In this study, a sub-millimeter-scale electrospun nanofiber patterning technique is proposed, which uses a functional electrolyte as a collector electrode between an electrospun nanofiber and a collector substrate. Adhesion between nanofibers and substrate is promoted by using polydopamine solution as a functional electrolyte. In this method, after the electrospinning process is completed, the electrolyte used as the collector electrode is evaporated so that the nanofiber and the substrate are in direct contact, without any trace of the metal electrode. Nanofibers can also be patterned on a thick insulator using this fabrication method. This fabrication method combines the advantages of conventional wet-electrospinning and electrospinning techniques with metal electrodes in terms of nanofiber patterning.