Poly L-lactic acid (PLLA) is a non-toxic, biocompatible degradable polymer material with excellent mechanical properties after molding. However, it faces challenges in the use of biomedical materials because of its intolerance to bacteria. Here, we use an easy-to-operate method to prepare a composite multilayer membrane: PLLA membrane was used as substrates to assemble positively charged chitosan and negatively charged Ag@MXene on the surface using the Layer-by-layer (LBL) method. The assembly process was detected by Fluorescein Isothiocyanate (FITC)-labelled chitosan and the thickness of the coating multilayer was also detected as 210.0 ± 12.1 nm for P-M membrane and 460.5 ± 26.5 nm for P-Ag@M membrane. The surface self-assembled multilayers exhibited 91.27% and 96.11% growth inhibition ratio against E. coli and S. aureus strains under 808 nm near-infrared (NIR) laser radiation with a synergistic photothermal antibacterial effect. Furthermore, best biocompatibility of P-M and P-Ag@M membranes compare to PLLA membrane motivated us to further explore its application in biomedical materials