Electrostatic spinning (Electrospinning, ES) was applied to prepare Donepezil HCl loaded nanofibers as a potential orally dissolving dosage form. Electrospinning of water solutions of different polymers were performed in order to fabricate a consistent and removable web on the collector with ultra-fast dissolution in water based media. Poly(vinyl-alcohol) of low molecular weight was found to be the most appropriate for this purpose. Morphology of the prepared nanofibers was characterized by scanning electron microscope as a function of viscosity and drug content. Diameters of the fibers were between 100 and 300 nm with narrow distribution. In vitro drug release of the webs was immediate (less than 30 s) after immersion independently of their drug content owing to the formed huge surface area, while cast films with the same compositions and commercial tablets needed 30 min or more for complete dissolution. The developed technology for the preparation of orally dissolving web (ODW) formulations is a promising way for producing effective and acceptable dosage forms for children, older people and patients with dysphagia.