This work demonstrated that unpurified suberin monomers, derived from a renewable side-stream, can be exploited to synthesize thin and flexible films. This was achieved following established extraction protocols followed by melt-polycondensation carried out in air, thus, with the absence of additional solvents or particular processing conditions. A conventional compression molding step followed by a curing period afforded the PEFA films. The 18-hydroxy-9,10-epoxy octadecanoic acid was found to be the main responsible for the polyester film formation, through a direct and ring-opening mechanism. Both could be followed during the processing by NMR and FT-IR spectroscopy. The triple functionality of the EFA monomer leads to the formation of cross-links, which cause a reduction in the glass transition heat-flow signal and drive the Tg to higher temperatures. Thus, from the DSC thermogram, the formation of a cross-linked polymer network is evident. Furthermore, the observed elastomer-like behavior during tensile testing is consistent with the cross-linked and amorphous nature of the films. The WVTR of the PEFA films was comparable to shorter chain polyesters but it could be potentially improved, by reducing the quantity of unreacted hydroxyl groups that remained in the film. The presence of NaCl crystals should also be addressed by adding a washing step after the EFA extraction. Nonetheless, the polyester film showed good water vapor barrier properties, low water uptake at 50 % relative humidity, and UV-blocking while being translucent. Furthermore, the lack of monomeric species capable of migrating from the film, as deduced from the TGA, suggests food packaging as an appropriate application for suberin-reconstructed films.