A hinged, photoresponsive polypeptide (PAzP) was prepared and the effect of the photochromic hinge on the dielectric and photoisomerization behavior of the polymer in solution was probed. Polymerization of N-carboxyanhydride of gamma -benzyl-L-glutamate was carried out with two different bifunctional photochromic amine initiators: di[(mercaptoethylamine)-methylpropanamide]azobenzene (DMMPAB) and diaminoazobenzene (DAAB). Careful structural comparison of the polymers revealed that the basicity of the initiator plays a key role in determining the shape and structure of the polymer. Specifically, the use of a novel initiator DMMPAB prepared by the addition of flexible aliphatic amine substituents onto DAAB resulted in a hinged polymer (PAzP1), in which a single photochromic hinge was located within the polymer chain (M-w similar to 36 kDa). In contrast, direct initiation with DAAB resulted in a polymer (PAzP2) in which the photochromic moiety was preferentially near the terminus of the polymer chain (M-w similar to 21 kDa) and the polymer possessed a significant degree of asymmetry. Dielectric spectroscopy revealed that, in spite of a higher molecular weight, PAzP1 had a lower rotational relaxation time (2.72 mus) in solution than that of PAzP2 (4.41 mus). The residual dipole moment for the hinged PAzP1 was also smaller than that observed for PAzP2. The hinged polypeptide PAzP1 prepared from DMMPAB showed uniform photoisomerization between cis and trans states. However, the presence of flexible aliphatic amine substituents on DMMPAB caused the rate of isomerization of PAzP1 to be similar to the initiator DMMPAB. Optical characterization revealed that heterogeneity in the structure of PAzP2 was manifested as nonuniform rates of photoisomerization and thermal relaxation.