Wound dressings play an indispensable role in wound healing. However, traditional wound dressings have several disadvantages, such as poor mechanical properties and small pore diameters, which do not allow sufficient gas exchange. To overcome these shortcomings, this paper reports a polyvinyl alcohol (PVA)-based hydrogel physically crosslinked at -20 °C and containing polyethylene glycol (PEG) and nanohydroxyapatite (HAP). The physical and chemical properties of the hydrogels formed by different stirring methods (stirring with a glass rod or a hand-held homogenizer) were compared. The average roughness of Gel 1 (prepared using a hand-held homogenizer) is 112.6 nm, which is much lower than the average surface roughness of Gel 2 (1222 nm, prepared using a glass rod). Moreover, the hydrogel made by the unconventional mixing method (with a homogenizer) showed better performance, including a more interconnected open-pore microstructure and better mechanical properties. Finally, a full-thickness skin defect test was performed. The experimental results demonstrated that the hydrogel has considerable potential for applications in wound dressings.