Reported is the enantioselective synthesis of tetracyclic indolines using silver(I)/chiral phosphoric acid catalysis. A variety of alkyne‐tethered indoles are suitable for this process. Mechanistic studies suggest that the in situ generated silver(I) chiral phosphate activates both the alkyne and the indole nucleophile in the initial cyclization step through an intermolecular hydrogen bond and the phosphate anion promotes proton transfer. In addition, further modifications of the cyclization products enabled stereochemistry–function studies of a series of bioactive indolines. Duality: Highly enantioselective synthesis of tetracyclic indolines was realized using cooperative silver(I)/chiral phosphoric acid catalysis. Mechanistic studies identified the dual role of the chiral phosphate. M.S.=molecular sieves.