Chronic wounds are prone to infections with multidrug-resistant bacteria, forming polymicrobial biofilms that limit treatment options and increase the risk of severe complications. Current cleansing options are insufficient to disrupt and remove tenacious biofilms; antibiotic treatments, on the other hand, often fall short against these biofilm-embedded bacteria. This study explores an non-antibiotic approach that extends beyond conventional porphyrin-based phototherapy by using blue light (BL) in conjunction with ferric ions (Fe(III)) to disrupt and eradicate biofilms. The dual not only degraded biofilm extracellular polymeric substances (EPS) in mono-species and polymicrobial biofilms by specifically targeting carboxyl-containing polysaccharides within the matrix but also exhibited broad-spectrum antimicrobial activity by affecting key components of the outer membrane and cell wall. Bacteria, such as K. pneumoniae, with compromised EPS after photolysis, demonstrated increased susceptibility to macrophage phagocytosis. Disruption of the polymicrobial biofilm structure also enhanced the bacterial susceptibility to bactericidal drugs. Treating wounds infected by mixed-species biofilm in diabetic mice demonstrated a substantial reduction in bacterial colonization and improved tissue repair. The BL-Fe(III) modality offers a safe, efficient alternative for managing chronic wound infections, making it ideal for repeated, non-invasive use at home, especially in resource-limited areas.