Photothermal synergistic antimicrobial therapy is considered a promising strategy to cope with antibiotic-resistant bacterial infections. In this work, lignin-based polydopamine nanosilver composites (LS-PDA-Ag) were engineered by a two-step process including self-assembly and microwave-assisted reduction. First, sodium lignosulfonate (LS) was not only used as a carrier to disperse polydopamine (PDA) and silver nanoparticles (AgNPs), but also used to reduce Ag+ for producing AgNPs. Second, PDA could promote the reduction of Ag+ and enhance the photothermal effect of AgNPs to further improve antibacterial efficiency. Finally, LS, AgNPs, and PDA complement each other, forming a synergistic photothermal antibacterial mechanism, achieving efficient bacterial killing within a short time. The antibacterial test of LS-PDA-Ag confirmed that 7.6 log10 CFU/mL of Escherichia coli were killed in 10 min under near-infrared irradiation. Furthermore, the LS-PDA-Ag can be blended with waterborne polyurethane to synthesize hybrid films, which also results in rapid sterilization and mechanical performance improvement. Considering the highly effective antibacterial activity of the LS-PDA-Ag composite, this work may provide perspectives on the design of green photothermal antibacterial materials.