The reactions of racemic and enantiopure macrocyclic compounds [Ni(alpha-rac-L)](ClO4)(2) (containing equal amounts of SS and RR enantiomers), [Ni(alpha-SS-L)](ClO4)(2), and [Ni(alpha-RR-L)](ClO4)(2) with K[Ag(CN)(2)] in acetonitrile/water afford three 1D helical chains of {[Ni(f-rac-L)][Ag(CN)(2)](2)}(n) (1), {[Ni(f-SS-L)](2)[Ag(CN)(2)](4))(n) (Delta-2), and {[Ni(f-RR-L)(2)-[Ag(CN)(2)](4)}(n) (Lambda-2); one dimer of [Ni(f-rac-L)][Ag(CN)(2)](2) (3); and one trimer of [Ni(f-rac-L)Ag(CN)(2)](3) center dot (ClO4)(3) (4) (L = 5,5,7,12,12,14-hexamethyl- 1,4,8,11 -tetraazacyclotetradecane). Compounds 1, Delta-2, Lambda-2, and 3, which are supramolecular isomers, are constructed via argentophilic interactions. In 1, [Ni(f-RR-L)][Ag(CN)(2)](2) enantiomers alternately connect with [Ni(f-SS-L)][Ag(CN)(2)](2) enantiomers through intermolecular argentophilic interactions to form a 1D meso-helical chain, and the 1D chains are further connected through the interchain hydrogen bonds to generate a 2D network. When chiral [Ni(alpha-SS-L)1(ClO4)(2) and [Ni(alpha-RR-L)](ClO4)(2) were used as building blocks, two supramolecular stereoisomers of Delta-2 and Lambda-2 were obtained, which show the motif of homochiral right-handed and left-handed helical chains, respectively, and the 1 D homochiral helical chains are linked by the interchain hydrogen bonds to form a 3D structure. In 3, a pair of enantiomers of [Ni(f-RR-L)][Ag(CN)(2)](2) and [Ni(f-SS-L))[Ag(CN)(2)](2) connect with each other through intermolecular argentophilic interactions to form a dimer. The reaction of [Ni(alpha-rac-L)](ClO4)(2) with K[Ag(CN)(2)] in acetonitrile gives a trimer of 4; each trimer is chiral with unsymmetrical RR, RR, and SS, or RR, SS, and SS configurations. The homochiral nature of Delta-2 and Lambda-2 was confirmed by the results of solid circular dichroism spectra measurements. The solid samples of 1-4 show strong fluorescent emissions at room temperature.