Two enantiomorphic (P and M) helical coordination polymers of [Cu(μ_1,3-N₃)(L)]_n {HL = 2-(dimethylamino)ethyliminomethylnaphthalen-2-ol} have been synthesized by the self-assembly of the achiral precursors via spontaneous resolution. The structures have been confirmed by single crystal X-ray crystallography. Solid-state circular dichroism spectra have confirmed the chirality of both P and M helical chains.