Continuous work and developments in biomedical materials used in three-dimensional (3D) bioprinting have contributed to significant growth of 3D bioprinting applications in the production of personalized tissue-repairing membrane, skin graft, prostheses, medication delivery system, and 3D tissue engineering and regenerative medicine scaffolds. The design of clinic products and devices focus on new natural and synthetic biomedical materials employed for therapeutic applications in different 3D bioprinting technologies. Design and characterization of natural and synthetic soft polymeric materials with biomimetic 3D microarchitecture were considered. The natural soft polymeric materials would focus on new design bioinspired membranes containing supercritical fluids-decellularized dermal scaffolds for 3D bioprinting potential applications. Synthetic soft polymeric materials would focus on bioinspired polyvinyl alcohol (b-PVA) matrix with structural foam-wall microarchitectures. Characterization, thermal stability, and cell morphology of the b-PVA and the corresponding collagen-modified b-PVA were employed to evaluate their potential tissue engineering applications. Also, the b-PVA materials were conductive to HepG2 cells proliferation, migration, and expression, which might serve as a promising liver cell culture carrier to be used in the biological artificial liver reactor. TGA, DTG, DSC, SEM, and FTIR were employed to build up the effective system identification approach for biomimetic structure, stability, purity, and safety of target soft matrix.