In this study, we synthesized a low-molecular-weight polytyrosine (PTyr) through living ring-opening polymerization of the alpha-amino acid-N-carboxyanhydride and then blended it with poly(4-vinylpyridine) (P4VP) homopolymer in N,N-dimethylformamide (DMF) and MeOH solutions, thereby controlling the miscibility behavior and secondary structures of the PTyr. Infrared spectroscopy revealed that the PTyr/P4VP mixture featured strong hydrogen bonds between the OH groups of PTyr and the pyridyl groups of P4VP. Differential scanning calorimetry revealed that the glass transition temperatures of the PTyr/P4VP complexes formed from MeOH solutions were higher than those of the corresponding PTyr/P4VP miscible blends obtained from DMF solutions. The behavior of the PTyr/P4VP blends obtained after evaporation of the DMF solutions was consistent with separated random coils of the PTyr chains. The increased degree of hydrogen bonding within the PTyr/P4VP complexes formed from MeOH solutions resulted in interpolymer complex aggregates; the corresponding enhanced intermolecular hydrogen bonding of PTyr with P4VP resulted in beta-sheet conformations for PTyr, as evidenced from Fourier transform infrared spectroscopy, solid state nuclear magnetic resonance spectroscopy, and wide-angle X-ray diffraction analyses. This model, which takes advantage of the well-defined secondary structures (alpha-helices, beta-sheets) of PTyr, can, therefore, be used to identity the behavior of separated coils and aggregated chains in polymer blend and complex systems.