A green process for the microwave-assisted hydrothermal selective dissolution and utilisation of hemicellulose in Phyllostachys heterocycla cv. Pubescens (shortened to pubescens) was developed. The process facilitated the efficient dissolution of hemicellulose at 200°C, while obtaining hemicellulose-free residue that could be further used as starting materials within many industrial processes. A variety of analytical techniques (e.g., HPLC, FT-IR, SEM, TG/TGA, Py-GC/MS, TG-IR, 13C liquid NMR, 2D HSQC NMR, and 13C CPMAS NMR analysis) were used for the analysis of the obtained liquid and solid products, which revealed that hemicellulose was completely extracted from pubescens. A solid residue left after this process consists of cellulose and lignin in a pure form and can be used for production of glucose and aromatic compounds. Interestingly, a new route to produce hemicellulose-based films that could potentially be used for food packaging was achieved. The developed approach opens avenue for a low-cost and sustainable bamboo-based biorefinery.