Novel supramolecular solids whose topologies depend on the counteranion, [Ag(C 14 H 20 N 6 )(NO 3 )] (1), [Ag(C 14 H 20 N 6 )]CF 3 SO 3 (2), and [Ag(C 14 H 20 N 6 )]ClO 4 (3), have been prepared by the self-assembly of AgX (X ) NO 3 -, CF 3 SO 3 -, and ClO 4 -) with ethylenediaminetetrapropionitrile (EDTPN, C 14 H 20 N 6 ). X-ray crystal structures indicate that compounds 1-3 are a 1-D coordination polymer, a 2-D layer, and a boxlike 2-D network, respectively. In 1, 2, and 3, the EDTPN ligand undergoes anion-dependent ligation to bind two, three, and five Ag(I) ions per EDTPN, respectively, by using the cyano groups in addition to two tertiary nitrogen atoms. The coordination numbers of Ag(I) ion in 1, 2, and 3, are five, four, and six, respectively. Interestingly, the CF 3 SO 3 -anion of 2 is exchanged with NO 3 -and ClO 4 -quantitatively in the crystalline state when the crystal of 2 is immersed in the aqueous solutions of NaNO 3 and NaClO 4 , respectively. The anion-exchange process is reversible between 1 and 2 but irreversible from 1 or 2 into 3. The supramolecular structural transformations among 1-3 are observed in the crystalline state, concomitant with the anion-exchange.