Herein, this study reports the development of a multifunctional conductive antibacterial cotton fabric through the utilization of the natural polyphenol-mediated silver mirror reaction. The experimental results demonstrate that polyphenols can effectively facilitate the deposition of silver nanoparticles (AgNPs), resulting in a uniform and durable hybrid nanocoating on the cotton fabric. The effects of polyphenol’s molecular weights on the coating structures and stabilities have been revealed via two distinct approaches: washing resistance and electrochemical testing systems. It has been concluded that lower-molecular-weight phenols induce a compact and dense coating structure, whereas polyphenols such as tannic acid exhibit relatively high stability, achieving an excellent conductivity of 0.2 S/cm and a good washing resistance of 67% over five cycles. The underlying mechanism has been further confirmed by the cyclic voltammetry measurements, suggesting that polyphenols play a significant role in stabilizing AgNPs and preventing their dissolution. Furthermore, the Ag-doped polyphenol-coated fabrics exhibit notable antibacterial properties. By coupling natural polyphenols with typical silver mirror reactions, this study not only offers a sustainable alternative to synthetic chemicals but also presents a promising method to endow cotton textiles with the dual properties of conductivity and antibacterial activity.