With the rise in antibiotic resistance (AR) and multidrug-resistant (MDR) bacteria, there is an urgent need for novel antimicrobials that can exert antibacterial action via multiple mechanisms. Nanoparticles such as silver nanoparticles (AgNP) can be a potential alternative due to their unique optical and physiochemical properties and innate broad-spectrum antibacterial activity. AgNPs antibacterial property is associated with the release of silver ions (Ag+), a slow process taking up to days to achieve effective antibacterial levels. Recent findings indicate combining photodynamic inactivation (PDI) with AgNP shows antibacterial synergy. This research aims to develop light-activable silver nanoparticles and investigate their light-responsive Ag+ release kinetics to understand their role in antibacterial synergy. Herein, protoporphyrin IX (PpIX) conjugated on the AgNP surface (PpIX-AgNP) was developed, and Ag+ release kinetics were investigated to correlate the Ag+ release kinetics to the antibacterial synergy of PS-AgNP. These PpIX-AgNPs serve as excellent light-activated antimicrobial agents, and this antibacterial action was demonstrated in gram-positive, Methicillin-resistant Staphylococcus aureus (MRSA) and gram-negative, multi-drug resistant (MDR) Escherichia coli. The antibacterial action of this light-activated PpIX-AgNP was further modulated by adopting a dual-step irradiation strategy to ensure the controlled release of Ag+. Finally, this research includes a preliminary study demonstrating the transport of nanoparticles within biofilms and light-activated inhibition of Vibrio cholerae biofilms. This research provides crucial knowledge for designing light-responsive silver-based antimicrobials for potential wound-healing applications.