1,2,5,6-Tetrasilabenzobenzvalene, a valence isomer of 1,2,3,4-tetrasilanaphthalene, was synthesized and structurally characterized by the coupling reaction of the dipotassium salt of the tetrasilacyclobutadiene dianion with o-dibromobenzene. The 1,2,5,6-tetrasilabenzobenzvalene was presumably obtained by the isomerization of the initially formed 1,2,3,4-tetrasilabenzo-1,4-Dewar benzene.