Xylan polysacccharides, both with and without acetyl substituents, were obtained from the specific hardwood Eucalyptus urograndis by controlled extraction processes and eventually post-acetylated. They were subsequently functionalized with well-defined levels of methacrylic monomers to thereby provide different degrees of substitution of the functional group. These modified xylans were the basis to successfully prepare for the first time xylan/poly(2-hydroxyethyl methacrylate)-based hydrogels via the radical polymerization of HEMA, used as a crosslinking agent. The tuning of the crosslinking density of the hydrogel network was accomplished by preparing hydrogels that had two composition ratios of xylan to HEMA (60 : 40 and 40 : 60) and was also done by varying the degrees of substitution. The resulting hydrogels were characterized according to their morphology, swelling and rheological properties by field emission scanning electron microscopy (FE-SEM), gravimetric measurements after immersion in water, and dynamical mechanical analysis. Surprisingly, the presence of acetyl moieties leads to stiffer hydrogels which have a reduced capacity for water uptake. A natural extension to the synthesis and characterization of the novel-based xylan hydrogels is examining one of their primary functionalities: encapsulation and release. This functionality was one of the drivers of this work when it was conceived given the inherent ability of hydrogels to act as cargo carriers. Therefore, a representative anticancer drug doxorubicin was loaded into these hydrogels and its release in different media was studied. Acetylated xylans showed high delivery ratios while non-acetylated samples leveled off at half the level of the acetylated samples.