When skin is injured, wound exudate is produced, and excessive exudate can impede the healing process. The management of exudate is particularly crucial in chronic wound healing. Among various dressings used for chronic wound care, research on highly absorbent aerogel-based dressings remains relatively limited. In this study, polyvinyl alcohol (PVA) aerogels were fabricated via vacuum freeze-drying under varying freezing conditions and precursor solution concentrations. The resulting aerogels exhibit excellent water absorption capacity, enabling timely removal of wound exudate, thereby addressing the challenge of impaired healing in chronic wounds caused by excessive exudate accumulation. The results indicate that a higher porosity and more regular pore structure contribute to improved water absorption performance of the aerogels. Further investigation reveals that both the precursor concentration and freezing conditions jointly govern the structure and properties of the PVA aerogels. Aerogels derived from low-concentration precursors exhibit inadequate network stability, whereas those from high-concentration precursors tend to become excessively dense. The aerogel prepared at a precursor concentration of 6 wt.% demonstrates an optimal balance of network structure and overall performance. Furthermore, a comparison of different freezing methods reveals that PVA aerogels prepared via directional freezing exhibit a more regular pore structure than those fabricated via non-directional freezing. This approach yields a pore structure characterized by a gradient variation in pore size along the cooling direction, which enhances the drainage efficiency of the aerogel dressings. This study elucidates the significant influence of preparation conditions on enhancing the water absorption capacity of PVA aerogels and highlights their potential for development as advanced high-absorbency wound dressings.