Wound dressing production represents an important segment in the biomedical healthcare field, but finding a simple and eco-friendly method that combines a natural compound and a biocompatible dressing production for biomedical application is still a challenge. Therefore, the aim of this study is to develop wound healing dressings that are environmentally friendly, low cost, and easily produced, using natural agents and a physical crosslinking technique. Hydrogel wound healing dressings were prepared from polyvinyl alcohol/carboxymethyl cellulose and sericin using the freeze–thawing method as a crosslinking method. The morphological characterization was carried out by scanning electron microscopy (SEM), whereas the mechanical analysis was carried out by dynamic mechanical analysis (DMA) to test the tensile strength and compression properties. Then, the healing property of the wound dressing material was tested by in vitro and ex vivo tests. The results show a three-dimensional microporous structure with no cytotoxicity, excellent stretchability with compressive properties similar to those of human skin, and excellent healing properties. The proposed hydrogel dressing was tested in vitro with HaCaT keratinocytes and ex vivo with epidermal tissues, demonstrating an effective advantage on wound healing acceleration. Accordingly, this study was successful in developing wound healing dressings using natural agents and a simple and green crosslinking method.