A novel segmented block copolymer, containing polyethylene glycol segment and GlyAlaGlyAla sequence derived from B. mori silk, has been prepared as a model for silk-based materials using both solution and interfacial techniques. Inherent viscosity, size exclusion chromatography, and light-scattering measurements gave molecular weight between M_w 34,000–39,000. Evidence for phase separation was provided by differential scanning calorimetry, which gave two T_g's at −57 °C and 111 °C, and transmission electron microscopy, which showed a morphology in which the peptide domain, estimated to be about 20–50 nm, was dispersed in the continuous polyether phase. Solid-state FTIR spectroscopic results showed that the polymer contained both parallel and antiparallel β-sheet stacks, and that the solution-polymerized material has the higher β-sheet content. This was further confirmed by ¹³C NMR, which gave about 80% total β-sheet content for the solution-polymerized product and about 40% for the polymer obtained by interfacial polymerization. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 352–366, 2000