Xylans, an important sub-class of hemicelluloses, represent a largely untapped resource for new renewable materials derived from biomass. As with other carbohydrates, nanocellulose reinforcement of xylans is interesting as a route to new bio-materials. With this in mind, birch wood xylan was combined with nanofibrillated cellulose (NFC) and films were cast with and without glycerol, sorbitol or methoxypolyethylene glycol (MPEG) as plasticizers. Microscopy revealed some NFC agglomeration in the composite films as well as a layered nanocellulose structure. Equilibrium moisture content in plasticized films increased with glycerol content but was independent of xylan:NFC ratio in unplasticized films. Sorbitol- and MPEG-plasticized films showed equilibrium moisture contents of approximately 10 wt% independent of plasticizer content. Tensile testing revealed increases in tensile strength with increased NFC content in the xylan:NFC composition range from 50:50 to 80:20 and plasticizer addition generally provided less brittle films. The oxygen permeability of unplasticized xylan-NFC films fell into a range which was similar to that for previously measured pure NFC films and was statistically independent of the xylan:NFC ratio. Water vapor permeability values of 1.9–2.8·10−11 g Pa−1 m−1 s−1 were found for unplasticized composite films, but these values were significantly reduced in the case of films plasticized with 10–40 wt% sorbitol.