The reactions of a racemic four-coordinated nickel(II) complex [Ni(alpha-rac-L)](ClO4)(2) (containing equal amount of SS and RR enantiomers) with l- and d-phenylalanine in acetonitrile/water gave two less-soluble six-coordinated enantiomers of {[Ni(f-SS-L)(/-Phe)](ClO4)), (Delta-1) and ([Ni(f-RR-L)(d-Phe)YClO4)}(4) (Lambda-1), respectively. Evaporation the remaining solutions gave two six-coordinated diastereomers of ([Ni-3(f-RR-L)(3)(/-Phe)(2)(H2O)](ClO4)(4)}(n) (a-2) and ([Ni-3(f-SS-L)(3)(d Phe)(2)(H2O)](ClO4)(4)}n (b-2), respectively (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, Phe(-) = phenylalanine anion). The reaction of [Ni(alpha-rac-L)](ClO4)(2) with dl-Phe(-) gave a conglomerate of c-1; in which, the SS and RR enantiomers preferentially coordinate to l- and d-Phe(-) respectively to give a racemic mixture of Delta-1 and Lambda-1, and the spontaneous resolution occurs during the reaction, in which each crystal crystallizes to become enantiopure. Removing Phe(-) from Delta-1 and Lambda-1 using perchloric acid gave two enantiomers of [Ni(alpha-SS-L)](ClO4)(2) (S-3) and [Ni(alpha-RR-L)](ClO4)(2) (R-3). Dissolving S-3 and R-3 in acetonitrile gave two six-coordinated enantiomers of [Ni(f-SS-L)(CH3CN)(2)](ClO4)(2) (S-4) and [Ni(f-RR-L)(CH3CN)(2)](ClO4)(2) (R-4), while dissolving [Ni(alpha-rac-L)](ClO4)(2) in acetonitrile gave a racemic twining complex [Ni(f-rac-L)(CH3CN)(2)](ClO4)(2) (rac-4). Delta-1 and Lambda-1 belong to supramolecular stereoisomers, which are constructed via hydrogen bond linking of [Ni(f-SS-L)(l-Phe)](+) and [Ni(f-RR-L)(d-Phe)](+) monomers to form 1D homochiral right-handed and left-handed helical chains, respectively. The reaction of S-3 with d-Phe- gave ([Ni(f-SS-L)(d-Phe)](ClO4)}(n) (5), which shows a motif of a 1D hydrogen bonded zigzag chain instead of a 1D helical chain. Compound a-2/b-2 contains dimers of [[Ni(f-RR-L))(2)(PPhe)(H2O)](3+)/ [[Ni(f-SS-L)}(2)(d-Phe)(H2O)](3+) and 1D zigzag chains of{I[Ni(f-RR-L)(l-Phe)](+))}(n)([Ni(f-SS-L)(d-Phe)](+))(n). The homochiral nature of Delta-1/Delta-1, a-2/b-2, S-3/R-3, and S-4/R-4 are confirmed by the results of circular dichroism (CD) spectra measurements.