In this study, a polysaccharide fragment with antioxidant and reactive oxygen species (ROS) scavenging activities was extracted from Maca (Lepidium meyenii Walp.) and subjected to structural analyses. The fragment, characterized by the α-D-Glcp-(1 → terminal group of the main chain linked to the →4)-Glcp-(1 → end unit through an O-6 bond and the O-3 bond of 1–3-4Glcp, was modified by introducing dialdehyde structures on its glucose units. It was then crosslinked with N-carboxymethyl chitosan via the Schiff base reaction to create a multifunctional hydrogel with antibacterial and ROS scavenging properties. Polyvinyl alcohol was incorporated to form a double crosslinked gel network, and the addition of silver nanoparticles enhanced its antibacterial efficacy. This gel system can scavenge excess ROS, mitigate wound inflammation, eradicate harmful bacteria, and aid in the restoration of skin microecology. The multifunctional maca polysaccharide hydrogel shows significant potential as a medical dressing for the treatment of infected wounds.