The invention discloses a quaternary electrical storage device, a preparation method thereof and a quaternary storage material. The electrical storage device comprises a substrate, an organic film and an electrode. The substrate is ITO glass modified by a polymer of 3,4-vinylenedioxythiophene and a polystyrene sulfonic acid blend. The quaternary organic electrical storage device provided by the invention has the advantages of low open voltage and high device yield. According to the invention, the modified electrical storage device breaks through traditional secondary storage, can unexpectedly realize organic quaternary storage, and realizes 0, 1, 2 and 3 quaternary data storage; the problem that an organic multi-system is realized through molecular synthesis and structure is avoided; a simple and effective policy is provided for realizing a multi-system; and the quaternary electrical storage device, the preparation method thereof and the quaternary storage material have a high application value in the future storage field.