A scaled-up prehydrolysis process was elaborated to demonstrate an industrially feasible operation step in a pulping process that generates a valuable side product in addition to the cellulose pulp. The valuable side product is aqueous process liquor, a softwood hydrolysate (SWH) herein produced in 60 L batches, and its components were recovered and utilized as materials. The process parameters were shown to influence the yield, composition, and quality of the obtained hydrolysates. Furthermore, the process conditions were shown to influence the ability of SWHs to form free-standing, foldable films in blends with either microfibrillated cellulose (MFC) or carboxymethyl cellulose (CMC). Films with oxygen permeabilities (OP) as low as 0.35 cm3 μm day-1 m-2 kPa-1 at 50% relative humidity, were produced from aqueous solutions providing a viable and green alternative to petroleum-based packaging barriers. The OPs were very low regardless of SWH film composition and upgrading conditions, whereas the films' tensile performance was directly controlled by the ratio of SWH to cocomponent.