Crystallization of silver trifluoroacetate from chloroform solutions containing triphenylphosphine sulfide affords a trigonal and a monoclinic form of a 6:4 complex {[CF3C(O)OAg](6)(Ph3PS)(4)} of C-2 symmetry with different amounts of chloroform in the crystals. With the Ph3PS Components as template molecules, the CF3C(O)OAg units are assembled to form a 6-membered metallacycle codetermined by metallophilic bonding and enclosed by a 24-membered ring [AgOCO](6). A complex of the type [LAgOC(O)CF3](2), with L representing the isocyanide ligand (P)TolSO(2)CH(2)NC, has been shown to have a conventional bicyclic structure with three-coordinate silver atoms engaged in transannular metallophilic interactions.