The reactions of enantiopure chiral ligands (+)/(−)-4,5-pinenepyridyl-2-pyrazine (LS/LR) with CuCl2·2H2O in CH3OH/CH2Cl2 solution led to the formations of one-dimensional homochiral enantiomeric pairs with the formula [Cu(LR/S)Cl2]n·2H2O (R-1 and S-1, the isomers containing the LR and LS ligands, respectively). The circular dichroism (CD) spectra verified their chiroptical activities and enantiomeric natures. Their structures have been determined by X-ray single-crystal analyses, showing stairway-like and mirror-symmetric features, which represent the first examples of homochiral metal complexes with stairway-like structures. The ferroelectric property measurement indicated that R-1 exhibits ferroelectricity with the remnant polarization (Pr) value of 0.02 μC cm−2 under an applied electric field of 6.1 kV cm−1 at room temperature. The magnetic investigation of R-1 showed a weak intrachain antiferromagnetic coupling between Cu(II)–Cu(II) ions mediated by pyrazine, which can be interpreted by a spin-polarization mechanism. All these results suggested that R-1 and S-1 are potential multifunctional molecule-based materials combining optical activity, ferroelectricity and magnetism within one molecule.