Abstract: | The self‐assembly of nanostructures is dominated by a limited number of strong coordination elements. Herein, we show that metal–acetylene π‐coordination of a tripodal ligand (L) with acetylene spacers gave an M3L2 double‐propeller motif (M=CuI or AgI), which dimerized into an M6L4 interlocked cage (M=CuI). Higher (M3L2)n oligomers were also selectively obtained: an M12L8 truncated tetrahedron (M=CuI) and an M18L12 truncated trigonal prism (M=AgI), both of which contain the same double‐propeller motif. The higher oligomers exhibit multiply entangled facial structures that are classified as a trefoil knot and a Solomon link. The inner cavities of the structures encapsulate counteranions, revealing a potential new strategy towards the synthesis of functional hollow structures that is powered by molecular entanglements. |