A facile synthetic route was developed to fuse furan rings to a dibenzosilole core for the construction of difurobenzosilole derivatives through an electrophilic double cyclization reaction. Only silafluorene derivatives with electron-donating groups on the periphery participated in this cyclization. Suzuki–Miyaura coupling and deiodination of the diiododifurobenzosiloles resulted in highly emissive silicon-bridged dibenzofuran compounds. These obtained compounds exhibited very high luminescent quantum yields (93 to about 99 %) and good thermal stability. Single crystals of the silicon-bridged dibenzofuran compound with a marginal phenyl group were easily grown and analyzed by single-crystal X-ray diffraction, whereas the deiodinated silicon-bridged dibenzofuran compound showed a high tendency to self-organize into 1D microfibers in various solvents such as hexane, toluene, and THF.