The bulk properties of poly(γ-benzyl-L-glutamate)-poly(ethylene glycol), PBLG-PEO, diblock copolymer were investigated. The helical transition from 7/2 to 13/5 for pure PBLG was at 120 oC while those of GE-1 and GE-2, which contain flexible PEO block 40 wt% and 60 wt% respectively, were shown at 135℃ on DSC experiments. FT-IR and XRD experiments were shown that the diblock copolymers maintained their α-helical structure in the temperature range between 25℃ and 175℃. Increasing relative size of coil part resulted in the increase of intermolecular packing distances. Due to well-maintained helical structure, lyotropic LC phases were observed for the PBLG-PEO block copolymer by the polarized optical microscope (POM). Especially, GE-3 copolymer, which has 12.5 wt% PEO contents, showed the smectic C phase. The competition of favorable aggregation energy between rod-rod and coil-coil, and unfavorable aggregation energy of rod-coil give rise to change the supramolecular structure in mixed solvent.