Currently, bacterial infection due to multi-drug-resistant bacteria is one of the foremost problems in public health. Photodynamic therapy plays a significant role against bacterial infection, without causing any side effects. But the photosensitizers are associated with many drawbacks, which lessen their photodynamic efficiency. In this context, the current study describes the synthesis of new metallocatanionic vesicles and employs them in photodynamic therapy. These vesicles were synthesized by using a single-chain cationic metallosurfactant (CuCPC I) and sodium oleate (NaOl) as an anionic component. These vesicles were characterized from conductivity, dynamic light scattering, zeta potential, field emission scanning electron microscopy, and confocal microscopy measurements. Methylene blue (MB) was used as a photosensitizer and its singlet oxygen quantum yield in the presence of these vesicles was determined by irradiating with 650 nm wavelength laser light. These vesicles play a dual-functional role, one helping in delivering the photosensitizer and the second doubling their singlet oxygen production capability due to the presence of metal ions. Antibacterial photodynamic therapy (aPDT) was studied against E. coli bacteria (Gram-negative bacteria). These vesicles also inherit their antibacterial activity and MB-encapsulated metallocatanionic vesicles on irradiation have shown 100% killing efficiency. In summary, we offer metallocatanionic vesicles prepared via a facile approach, which encapsulate a photosensitizer and can be used to combat E. coli infection through photodynamic therapy. We envisage that these synthesized metallocatanionic vesicles will provide a new modification to the catanionic mixture family and could be used for various applications in the future.