Two hemicelluloses (HCs), galactoglucomannan (GGM) and arabinoglucuronoxylan (AGX), and nanofibrillated cellulose (NFC) were isolated from spruce wood and used for the preparation of composite films containing high amounts of cellulose, i.e. 85 and 80 wt% of NFC, respectively. The films were prepared in two ways: (i) by the pre-sorption of HCs on NFC and (ii) by the mixing of components in the usual way. Pre-sorption was applied in an attempt to mimic the carbohydrate biosynthesis pattern during wood cell wall development, where HCs were deposited on the cellulose fibrils prior to lignification taking place. It was assumed that pre-sorption would result in a better film-forming as well as stronger and denser composite films. The mechanical, thermal, structural, moisture sorption and oxygen barrier characteristics of such composite films were tested in order to examine whether the performance of composite films prepared by pre-sorption was better, when compared to the performance of composite films prepared by mixing. The performance of composite films was also tested with respect to the HCs used. All the films showed quite similar barrier and mechanical properties. In general, stiff, strong and quite ductile films were produced. The moisture sorption of the films was comparably low. The oxygen barrier properties of the films were in the range of commercially used poly ethylene vinyl alcohol films. However, the pre-sorption procedure for the preparation of composite films resulted in no additional improvement in the performance of the films compared to the corresponding composite films that had been prepared using the mixing process. Almost certainly, the applied mixing process led to an optimal mixing of components for the film performance achieved. The GGM contributed to a somewhat better film performance than the AGX did. Indications were observed for stronger interactions between the GGM and NFC than that for the AGX and NFC.