Freezing-thawing (F-T) cycles approach was applied for loading caffeic acid to physically-crosslinked hydrogel membranes composed of PVA/chitosan/caffeic acid (PVA-CS-CA). Three F-T cycles were carried out to guarantee the entanglement of PVA-CS-CA chains. Several instrumental characterizations were used to confirm and characterize the entanglements of polymeric chains. Physicochemical parameters of PVA-CS-CA membrane including swelling ratio (%), mechanical properties, gel fraction (GF%), hydrolytic degradation (%), and thermal stability, were thoroughly examined. Findings demonstrated that GF% gradually decreased with increasing CS content in the membrane composition, while mechanical characteristics, swelling ratio (%), and hydrolysis of the crosslinked materials improved. Furthermore, MTT assay and bacterial inhibition of growth percentage method were utilized to assess the antimicrobial characteristics towards Staphylococcus aureus and E. coli, respectively, and the cell viability test utilizing HFB-4 cell line. Interestingly, all of hydrogels investigated demonstrated noteworthy cell survival percentages with various incubation durations and membrane concentrates. The findings supported the hypothesis that hydrogel films might be used as biomaterials to promote quick wound healing or as antibacterial dressings in a professional setting.