The electrospinning of stereocomplex nanofibers of high-molecular-weight poly(L-lactic acid) (PLLA)/poly(D-lactic acid) (PDLA) (PLLA/PDLA = 1:1) was carried out with chloroform as the spinning solvent. The stereocomplex nanofibers with diameters of 830-1400 and 400-970 nm were successfully obtained at voltages of -12 and -25 kV, respectively. Wide-angle X-ray scattering indicated that with an increasing absolute value of voltage from 0 to 25 kV the crystallinity of homo-crystallites composed of either PLLA or PDLA decreased from 5% to 1%, whereas the crystallinity of stereocomplex crystallites increased slightly from 16% to 20%. The obtained results reveal that electrospinning is an effective method to prepare stereocomplex nanofibers with a negligibly small amount of homo-crystallites, even when high-molecular-weight PLLA and PDLA are used, and that the orientation caused by high voltage (or electrically induced high shearing force) during electrospinning enhances the formation and growth of stereocomplex crystallites and suppresses the formation of homo-crystallites.