In the present study, the aim was to synthesize free-standing polyester films starting from un-purified suberin monomers to reconstruct the biopolymer structure and mimic its properties, while exploiting simple and common processing techniques, such as meltpolycondensation in air and thermoforming (compression molding). The bark was subjected to a series of extractions to remove firstly betulin and secondly polysaccharides from the suberin. Thus, the process was placed within the frame of a possible bio-refinery, where most of the other components of the bark are extracted and exploited. Then, the retrieval of the EFA was performed through alkaline hydrolysis of the suberin, and a new protocol was designed to produce thin and flexible polyester films. Infrared and nuclear magnetic resonance spectroscopy were used to characterize the extracted EFA and follow the polyester formation. Meanwhile, the thermal stability, crystallinity, and mechanical properties of the final films were evaluated by employing X-ray diffraction, thermogravimetry, differential scanning calorimetry, tensile testing, and dynamic mechanical analyses. Lastly, the water vapor transmission rate was measured and the total transmittance of ultraviolet-visible light was evaluated.