In this work, a multi-layer wound dressing consisting of polyvinyl alcohol (PVA) foam and electrospun sodium carboxymethylcellulose (CMC) surface mesh was developed and characterized. Antimicrobial drug stearyl trimethyl ammoium chloride (STAC) was loaded into the PVA foam for infection control and the CMC surface mesh offers effective hemostatic function. Additionally, the potential of laser photodynamic response of the loaded methylene blue (MB) and its effect in enhancing the wound dressing’s bacterial inhibition has been investigated. The antibacterial drug and laser photodynamic therapy (PDT) were jointly deployed, which demonstrated greater potential in killing both S. aureus and E. coli bacteria strains. In addition, the unique color changing property of MB has enabled real time bacterial infection monitoring of the wound dressing. The multi-layer wound dressing with ideal material combination and unique multifunctionality may be a promising option for wound management in the future healthcare sector.