There are many modern wound dressings that have promising properties for repairing skin damage. However, due to various types of wounds and the problems they cause, there is still a great demand for new, effective healing strategies. The aim of this study was to create superabsorbent wound dressing made of marine-derived polysaccharides (agarose and chitosan) using the freeze-drying method. The secondary goal was its comprehensive evaluation for potential use as an external superabsorbent bandage for wounds with high exudation. Due to the well-known positive effect of ascorbic acid (vitamin C) on the healing process, biomaterial enriched with vitamin C was prepared and compared to the variant without the addition of ascorbic acid. It was shown that the produced foam-like wound dressing had a very porous structure, which was characterized by hydrophilicity, allowing a large amount of human fluids to be absorbed. According to in vitro tests on human fibroblasts, biomaterial was nontoxic and supportive to cell proliferation. Vitamin C-enriched dressing also had the ability to significantly reduce matrix metalloproteinase-2 production and to promote platelet-derived growth factor-BB synthesis by fibroblasts, which is desired during chronic wound treatment. The material has features of the eco-friendly wound care product since it was made of naturally-derived polysaccharides and was proved to be biodegradable. Importantly, despite degradable character, it was stable in the chronic and infected wound microenvironment, maintaining high integrity after 8-week incubation in the enzymatic solutions containing lysozyme and collagenases. The obtained results clearly showed that developed biomaterial possesses all necessary features of the external dressing for the management of exudate from both acute and chronic non-healing wounds.