We have synthesized heterochiral dodecadeoxynucleotides having an unnatural L-nucleotide residue, and have investigated their structures by ultraviolet (UV) absorption, circular dichroism (CD) measurements and nuclear magnetic resonance (NMR) spectroscopy. It was clearly shown that the overall structures of the heterochiral 12-mers are a right-handed B-conformation and the unnatural L-nucleotide residue in the heterochiral 12-mer (L-4) forms stable Watson-Crick type base-pairing with the natural complementary residue. In this double helix (L-4), the unnatural G4 residue has an S-type sugar conformer and a low-anti glycosidic torsion angle. From the properties of an enantiomer, natural nucleotides may possibly form a low-anti left-handed B-form duplex with the aid of certain factors.