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Herein, a series of metal\u2010phenolic network with Pd nanoparticle nodes using polyphenols as stabilizers and reducing agents is constructed. Among them, sulfonated lignin\u2010Pd (SLS\u2010Pd) with ultrafine size palladium nanoparticles and broadband near infrared absorption exhibit excellent oxidase\u2010like activity and stable photothermal effect. In vitro experiments demonstrate that the superoxide radical generated by SLS\u2010Pd oxidase\u2010like activity exhibits selective antibacterial effects, while its photothermal effect induced hyperthermia exhibits potent antifungal properties. This difference is further elucidated by RNA\u2010sequencing analysis and all\u2010atom simulation. Moreover, the SLS\u2010Pd\u2010mediated synergistic antimicrobial system exhibits remarkable efficacy in combating various biofilms and polymicrobial biofilms. By establishing a root canal model and an oropharyngeal candidiasis model, the feasibility of the synergistic antimicrobial system in treating oral biofilm\u2010related infections is further validated. 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