Damaged tissue with an open wound is one of the daily injuries and can have different levels of severity. Inspired by the textile dyeing, coloration and skin care effect of pyrogallol-rich red wine, tannic acid–KH561 (TA561) copolymer was fabricated by phenol–silanol reaction and polycondensation of silane in an aqueous medium under mild conditions. This copolymer could undergo sol–gel transition via continuous heating or when simply placed at room temperature, during which liquid TA561 oligomers connected with each other to form solid TA561 as a bulk resin or thin film. Combining the advantages of the polyphenols and polysiloxane, TA561 can be used as an adhesive for multiple surfaces, including wood, polytetrafluoroethylene, poly(vinyl chloride), aluminum chips and silicon rubber. Furthermore, TA561 also possessed reducing activity towards Ag⁺ or Au³⁺ ions to form the corresponding nanoparticles. An in vivo antimicrobial ability test indicated that TA561 could promote wound healing and showed resistance to methicillin-resistant Staphylococcus aureus (MRSA) infection in comparison with KH561. Indeed, TA561 has the potential to be utilized as a low-cost, green bioadhesive material for skin preparations.