This work focuses on the functionalization of agave xylan-type hemicellulose functionalized with trimethoxysilylpropylmethacrylate and crosslinked with N-vinylcaprolactam to obtain a thermoresponsive material for potential applications in drug delivery. The hydrogels showed an interconnected and porous architecture with a lower critical solution temperature (LCST) close to poly(N-vinylcaprolactam)’s (PNVCL) LCST. These materials showed a good capacity to load ciprofloxacin (in the range 9.5 × 10−3–8.4 × 10−3 mg/mL), above the minimum inhibitory concentration (MIC ≤ 0.004 × 10−3–0.5 × 10−3 mg/mL) for gram-positive and gram-negative bacteria. The hybrid hydrogel inhibited the growth of Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa.