Bis (ethylenedioxy)‐1,4,5,8‐tetraselenanaphthalene (BEDO‐TSeN) has been synthesized by the reaction of diselenolate with tetraiodoethylene or tetrabromoethylene. The structure of BEDO‐TSeN was determined by X‐ray analysis, and its π‐donor property was estimated by MO calculations and determined by CV analysis.