A pair of enantiomers formulated as {Δ-cis-[Ni(en)2OAc][ClO4]} n (Δ-1) and {Λ-cis-[Ni(en)2OAc][ClO4]} n (Λ-1) (en = diaminoethane, OAc− = acetate anion) were obtained when nickel acetate was reacted with diaminoethane and sodium perchlorate in the absence of any chiral source, whereas the reactions of nickel acetate with 1,3-propanediamine and sodium perchlorate only gave a centrosymmetric complex [Ni(1,3-pn)2OAc][ClO4] (2) (1,3-pn = 1,3-propanediamine). Single-crystal X-ray diffraction analyses of all three complexes indicated that the central Ni(II) atoms all have a distorted octahedral coordination geometry, being coordinated by four nitrogen atoms of the diamine ligands, plus two oxygen atoms of OAc−. In complexes Δ-1 and Λ-1, the monomers of {Δ-cis-[Ni(en)2OAc]}+ and {Λ-cis-[Ni(en)2OAc]}+ are connected through intermolecular hydrogen bonds to generate one-dimensional right- and left-handed homochiral helical chains, respectively, while the monomers of [Ni(1,3-pn)2OAc]+ are linked by similar intermolecular hydrogen bonds to form one-dimensional zigzag chains instead of helical chains. The chiral natures of complexes Δ-1 and Λ-1 have been confirmed by circular dichroism spectroscopy.