We have synthesized by solution methods and fully characterized a variety of (alpha Me)Leu/Aib model peptides to the octapeptide level. A solution conformational analysis was performed by using infrared absorption. 1H nuclear magnetic resonance, and circular dichroism. The crystal-state structures of Z-D-(alpha Me)Leu-(Aib)2-OtBu, pBrBz-(Aib)2-D-(alpha Me)Leu-(Aib)2-OtBu, and Ac-(Aib)2-D-(alpha Me)Leu-(Aib)2-OtBu monohydrate were solved by x-ray diffraction. The results indicate that the (alpha Me)Leu residue may be easily incorporated into beta-bends and 3(10)-helical structures, and suggest that this residue tends to induce a helix handedness opposite to that promoted by its unmethylated counterpart (Leu) of the same optical configuration.