In this study, β -D-xylopyranose has been proposed as a structural motif to model hemicellulose. Initial reaction steps, including ring opening, ring contraction, and dehydration, were investigated using quantum chemical calculations. Energetic results align well with previous literature findings and provide new reference data at the junChS level of theory. These data can serve as a valuable benchmark for future studies. Additionally, TST results will aid in the development of a global kinetic scheme for xylose pyrolysis in future research.