The copolymers of poly(amino acid)-urethane (PAU) with multiblock-triblock structures have been synthesized in N,N-dimethylformamide (DMF). The use of triethylamine as an initiator of polymerizing NCA to both terminals of the PAU intermediate having urethane segments and a small amount of PMLG caused gelatinization, while the use of hydrazine gave a fluid solution with a whitish turbidity. Infrared (IR) spectra of the PAU in DMF demonstrated that the PMLG segments in the PAU obtained from TEA had an alpha-helix structure and PAU from hydrazine had a beta-structure in addition to the alpha-helix structure. The X-ray diffraction pattern showed that the alpha-helix chains of the PMLG segments in the PAU obtained from hydrazine were oriented. Compared with the PMLG homopolymer, the elastic recovery and adhesion of the PAU significantly increased with a maintenance of a good sense of touch which is a unique quality of PMLG.