Cross-coupling reactions (e.g., Suzuki, Negishi, Heck, Stille, Kumada, and Buchwald-Hartwig reactions) are of paramount importance and have proven useful for the design of molecules. [1] Although cross-coupling reactions can precisely construct new C À C, C À X, and X À X bonds (X = heteroatom), they usually utilize preactivated substrates (e.g., halides, tosylates, and triflates) and require transmetalation steps, which concurrently generate at least stoichiometric amounts of metal salts as waste. [1] Recently, cross-dehydrogenative coupling reactions by direct activation of CÀH or XÀH bonds have been emerging as synthetic tools because they are more atom efficient and environmentally benign than classical cross-coupling reactions. [2] To date, several efficient crossdehydrogenative coupling reactions using hydrogen acceptors (oxidants) such as tert-butyl hydroperoxide, [3] hydrogen peroxide, [4] and molecular oxygen [5] have been developed. Acceptorless cross-dehydrogenative coupling reactions have also been developed. [6] Quite recently, we have also reported C À N (terminal alkynes and amides), [7] P À N (H-phosphonates and amides), [8] SiÀN (hydrosilanes and indoles), [9] and SiÀC (hydrosilanes and terminal alkynes) [10] bond-forming reactions by cross-dehydrogenative coupling strategy. Herein, we successfully developed a novel green synthetic route to silyl isocyanates through heterogeneous-gold-catalyzed, acceptorless cross-dehydrogenative coupling of hydrosilanes and isocyanic acid (generated by in situ thermolysis of urea [11] ) [Eq. (1)].