The objective of this study was to create oxygen barrier films based on the hemicellulose O-acetylgalactoglucomannan (AcGGM) that show high resistance toward moisture-rich conditions. We have applied Williamson benzylation, a classic derivatization method of carbohydrates, as well as two different methods for surface grafting, and, finally, lamination of unmodified hemicellulose films with the synthesized hydrophobic benzylgalactoglucomannan (BnGGM). It was found that the thermoplastically behaving BnGGM could form independent transparent and strong films that were easy to handle. As expected, their resistance toward water was very high, and the oxygen barrier properties showed drastically lower sensitivity toward moisture than films from the corresponding unmodified material. The surface grafting and lamination methods were approached in order to try and combine excellent barrier properties with moisture tolerance. It was found that the grafting methods applied had a positive effect in this direction; however, lamination turned out to be an even more promising option.