Based on the environmental concerns, the utilisation of hemicelluloses in food packaging has become a sustainable alternative to synthetic polymers and an important method for the efficient utilisation of biomass resources. After cellulose, hemicellulose is a second component of agricultural and forestry biomass that is being taken advantage of given its abundant source, biodegradability, nontoxicity and good biocompatibility. However, due to its special molecular structure and physical and chemical characteristics, the mechanical and barrier properties of hemicellulose films and coatings are not sufficient for food packaging applications and modification for performance enhancement is needed. Even though there are many studies on improving the hydrophobic properties of hemicelluloses, most do not meet environmental requirements and the chemical modification of these biopolymers is still a challenge. The present review examines emerging and green alternatives to acetylation for xylan hemicellulose in order to improve its performance, especially when it is used as biopolymer in paper coatings or films for food packaging. Ionic liquids (ILs) and enzymatic modification are environmentally friendly methods used to obtain xylan derivatives with improved thermal and mechanical properties as well as hydrophobic performances that are very important for food packaging materials. Once these novel and green methodologies of hemicellulose modifications become well understood and with validated results, their production on an industrial scale could be implemented. This paper will extend the area of hemicellulose applications and lead to the implementation of a sustainable alternative to petroleum-based products that will decrease the environmental impact of packaging materials.