Deeper in the blue: A versatile procedure has been developed for the preparation of photoluminescent siloles and germoles by palladium‐catalyzed cross‐coupling of 2,2′‐diiodobiaryls with dihydrosilanes and ‐germanes. The dibenzosiloles and ‐germoles with ester moieties on the aromatic ring exhibited different emission wavelengths in the solution and crystalline states, attributable to the intermolecular