The present invention relates to bipolar bisthieno[3,2-b:2',3'-d] thiophene derivatives and applications thereof. According to the derivatives, bisthieno[3,2-b:2',3'-d] thiophene groups serve as a center; by oxidation of the sulfur atom at site 4 to form bisthieno[3,2-b:2',3'-d] thiophene-4-oxides and bisthieno[3,2-b:2',3'-d] thiophene-4,4-dioxides, the electron transport property of bisthieno[3,2-b:2',3'-d] thiophene is improved; and simultaneously, a carbazole derivative or an aromatic amine compound having a good hole transport property is respectively introduced into 2 and 6 sites of the oxidized bisthieno[3,2-b:2',3'-d] thiophene, combining the advantages of both. By regulating the molecular structures of different parts of the molecule, the bisthieno[3,2-b:2',3'-d] thiophene derivatives is allowed to have hole and electron transport properties to form a bipolar transport material. The bipolar bisthieno[3,2-b:2',3'-d] thiophene material has a twisted non-planar spatial structure, thus effectively preventing tight accumulation of molecules. Experimental results show that the material of the invention has a high thermal stability and a glass transition temperature, and the material is separately used as an electron transport material, a hole transport material and a luminescent material for organic electroluminescent devices, electroluminescence with very high color purity and efficiency can be obtained.