In this study, we synthesized two forms of the polypeptidebased rod-coil diblock copolymer poly(ethylene oxide-b-gamma-benzyl-L-glutamate) (PEO-b-PBLG), comprising hydrophilic PEO as the coil segment and hydrophobic PBLG as the rod segment, with different degrees of polymerization (DPs) of the PBLG segment (DP = 20 and 45), through ring-opening polymerization of N-carboxyanhydride with amino-terminated PEO as the macroinitiator. Fourier transform infrared (FTIR) spectroscopy revealed the secondary structures of the resultant PEO-b-PBLG block copolymers with an alpha-helical conformation, while wide-angle X-ray diffraction (WAXD) revealed a hexagonally packed cylinder structure for the PBLG segments. When we blended the diblock copolymers with a resol-type phenolic resin at various compositions, FTIR spectra suggested that the resol OH groups preferred to hydrogen-bond with the ether oxygen atoms of the PEO segment, rather than with the C=O groups of the PBLG segment. At high resol contents, the crystalline structure of the PEO segment was destroyed, while the alpha-helical conformation and hexagonal cylinder structure of the PBLG segment remained unchanged, as determined using differential scanning calorimetry, FTIR spectroscopy, and WAXD. We prepared a series of microporous carbons through thermal calcination of resol/PEO-b-PBLG blends at various compositions. The microstructures of the resulting carbons were strongly influenced by the secondary structure of the PBLG segments, rather than the microphase separation of the block segments, in the resol/PEO b-PBLG blends. These microporous carbons exhibited an extremely high supercapacitor performance, with massive specific capacitances (up to 758.4 F g(-1) at a current density of 0.5 A g(-1)) and excellent stabilities (up to 97.32% after 2000 cycles at a current density of 10 A g(-1)).