Agronomic practices and the winemaking process lead to the production of considerable quantities of waste and by-products. These are often considered waste with negative effects on environmental sustainability. However, vine shoots and grape stalks can be reused, representing a potential source of xylo-oligosaccharides and polyphenols. In this context, the purpose of this work was to obtain enriched extracts using three different autohydrolysis treatments with (i) H2O, (ii) H2O:EtOH, and (iii) H2O:Amberlyst. The obtained extracts were characterized by their xylo-oligosaccharide and polyphenol profiles using LC-MS techniques. The use of ethanol during autohydrolysis allowed for greater extraction of xylan-class compounds, especially in vine shoot samples, while an increase in antioxidant activity (128.04 and 425.66 µmol TE/g for ABTS and DPPH, respectively) and in total phenol content (90.92 mg GAE/g) was obtained for grape stalks.