Commercial inexpensive preparations of poly-γ-glutamic acid were used to obtain films made with a polypeptide constituted by a single repeating unit. The homopolymer was characterized by 1H-NMR spectroscopy and thermogravimetry, as well as by zeta potential and Z-average measurements. Manipulatable materials were obtained by casting film-forming solutions prepared at pH values between 3.0 and 4.0 and containing extensively dialyzed samples of the commercial product. The analysis of the mechanical properties highlighted a marked extensibility and plasticity of the films obtained without plasticizer, even though the addition of low amounts of glycerol (1–4%) was able to further increase these features. The characterization of poly-γ-glutamic acid molecular species, performed by membrane ultrafiltration and size-exclusion chromatography, coupled with triple-detection analysis of the obtained fractions, suggested that biopolymer chain length is responsible not only for its capacity to form film, but also for conferring to the films di erent features depending on the homopolymer molecular weight.