Abstract A novel electrocatalyzed method for the preparation of dibenzosiloles was developed through intramolecular C−H/Si−H dehydrogenative coupling strategy starting from biarylhydrosilanes. Both electro‐donating and electro‐withdrawing substitution groups were tolerated for this transformation, and the desired dibenzosilole products could be obtained in moderate to excellent yields. A sila‐Friedel‐Crafts reaction mechanism was proposed on the basis of previous literature and our controlled experiments. magnified image