In the last decades, the production of value-added products from lignocellulosic biomass (LCB) has gained relevance. Xylans, which are the main hemicellulose compounds in LCB, may be extracted by alkaline pretreatment and employed for xylooligosaccharide (XOS) production. However, xylan extraction currently works as a black box due to the lack of characterization of the involved streams. Therefore, the appropriate operational conditions often remain unclear, especially in hardwoods. In this study, alkaline/thermal pretreatments at different operational conditions were evaluated for xylan extractions from Chilean Nothofagus species sawdust, determining the chemical compositions of the fractions at each step of the process. Results indicated that increasing alkali concentration (NaOH) leads to a higher xylan extraction, but also to high salt production during the acid neutralization step, decreasing xylan's purity and therefore XOS production. In this context, decreasing NaOH concentration and neutralizing it by membrane filtration, allow extracting xylans (62.5 %) of higher-purity (77 %).