Upon treatment of red, amorphous selenium with the silver salts of two large weakly coordinating anions (WCA), the thermodynamically driven formation of [Ag₂Se₁₂]²⁺ occurred. The structure of the dication is an unprecedented D₃d-symmetric 14-vertex cage built from six six-membered rings in a boat conformation that includes a weak argentophilic Ag–Ag bond.