The design and synthesis of homochiral double helicates are reported that are constructed by means of Ag‐induced supramolecular self‐sorting of saddle‐shaped cyclooctatetrathiophene‐based pyridine ligands (1 and 2). The intramolecular S⋅⋅⋅N interaction ensures that the thiophene and pyridine rings of ligands 1 and 2 are in coplanar and syn‐locked structures. In the presence of Ag+, the racemic ligands 1 and 2 only afforded homochiral double helicates, indicating effective chiral self‐sorting process under the influence of the S⋅⋅⋅N interaction. The X‐ray crystal structure of 12Ag2 reveals a pair of homochiral double helicates (R,R,R,R)‐12Ag2 and (S,S,S,S)‐12Ag2. Furthermore, chiral resolution of racemic ligand 1 was achieved by chiral‐phase HPLC, and the enantiomers and their corresponding enantiopure Ag complexes were characterized.