This study reports in vitro reconstitution of the development of type I collagen/PVA biomimetic hydrogels with good operability and stability by the freeze-thaw technique. To improve performances, the hydrogels were hybridized by biomimetic collagen type I. Structure and morphology were characterized with FT-IR, DSC and SEM. FT-IR spectrum and DSC thermograms of collagen/PVA hydrogels showed peaks that shift to lower peaks than PVA hydrogels and a higher peak than collagen hydrogels because of the complicated structure inside the hydrogels. The morphology observed by SEM showed that collagen mimicked into fibrils and formed a network structure and hybridized with PVA texture as the structure of skin. Therefore, the collagen/PVA hydrogels scaffold might be well suited for skin engineering of wound healing.