A polymer/solvent system can form a gel due to specific interactions between the polymer and the solvent. For poly-benzyl-L-glutamate/solvent systems, gelation can be based on carbonyl or phenyl ring interactions, depending on the solvent. The present paper describes X-ray scattering and Raman investigations on cast films of poly-benzyl-L-glutamate (PBLG) and benzylmethacrylate (BzMA). The studies indicate that in the cast samples separate zones of PBLG and BzMA are present. Upon heating, the system homogenises and the PBLG molecules pack in a pseudo hexagonal lattice. At approximately 150°C a new reflection at 11.4 Å in the WAXS pattern arises. This reflection is attributed to structural ordering of the solvent, due to intercalation of the solvent molecules within the helices of PBLG. The observed changes in the WAXS pattern upon heating are supported by Raman experiments.