The interests in the biomedical impact of tannic acid (TA) targeting production of various types of biomaterials, such as digital microfluids, chemical sensors, wound dressings, or bioimplants constantly increase. Despite the significant disadvantage of materials obtained from natural-based compounds and their low stability and fragility, therefore, there is an imperative need to improve materials properties by addition of stabilizing formulas. In this study, we performed assessments of thin films over TA proposed as a cross-linker to be used in combination with polymeric matrix based on chitosan (CTS), i.e. CTS/TA at 80:20 or CTS/TA at 50:50 and poly(ethylene glycol) (PEG) at the concentration of 10% or 20%. We evaluated their mechanical parameters as well as the cytotoxicity assay for human bone marrow mesenchymal stem cells, human melanotic melanoma (MNT-1), and human osteosarcoma (Saos-2). The results revealed significant differences in dose-dependent of PEG regarding the maximum tensile strength (σmax) or impact on the metabolic activity of tissue culture plastic. We observed that PEG improved mechanical parameters prominently, decreased the hemolysis rate, and did not affect cell viability negatively. Enclosed data, confirmed also by our previous reports, will undoubtedly pave the path for the future application of tannic acid-based biomaterials to treat wound healing.