Electrospinning and post-spun conformations of hydrophobic poly(α-amino acid)s are described in this study. The poly(α-amino acid)s, poly(Gly), poly(L-Ala), poly(L-Val), and poly(L-Leu) were synthesized via corresponding N-carboxy-a-amino acid anhydrides. The average molecular weight and degree of polymerization of these polymers were determined by N-terminus labeling using 2,4-dinitrofluorobenzene and by viscometry in the case of poly(Gly). These poly(α-amino acid)s were electrospun from trifluoroacetic acid or trifluoroacetic acid/dichloromethane solutions. The FT-IR spectroscopy and wide-angle X-ray diffraction indicated that the electrospun poly(L-Ala) and poly(L-Leu) fibers predominantly adopts α-helical structure, whereas poly(L-Val) and poly(Gly) fibers exhibited mainly β-strand and random coil structures, respectively.