Antibiotic-resistance (ABR) poses a critical public health challenge within the broader antimicrobial resistance crisis. This review evaluates the potential of polyelectrolytes (PEs) and polyelectrolyte complexes (PECs) for controlled antibiotic delivery as a strategy to combat ABR and biofilm-related infections. PECs, particularly those incorporating chitosan and other polycations, enhance antibacterial efficacy by disrupting bacterial cell walls and obstructing their nutrient flow. They are also effective in penetrating biofilms and providing sustained drug release. Despite these advantages, there is a need for further in vivo research and clinical trials to validate these findings. This review provides a comprehensive overview of PECs’ potential to advance antibacterial therapies and outlines future research directions to further explore their applications.