The product of ozonolysis, Glycero-(9,10-trioxolane)-trioleate (ozonide of oleic acid triglyceride, [OTOA]), was incorporated into polylactic acid/polycaprolactone (PLA/PCL) blend films in the amount of 1, 5, 10, 20, 30, and 40% w/w. The morphological, mechanical, thermal and antibacterial properties of the biodegradable blend after the OTOA addition were studied. According to DSC and XRD data, the crystallinity degree of PLA/PCL+OTOA films tended to decrease with increase in OTOA content that could be explained by its plasticizing effect. Morphological analysis showed that the structure of the films with the OTOA concentration above 20% drastically changed. Specifically, the interface between the PLA/PCL matrix and OTOA was formed, thereby forming a capsule with the embedded antibacterial agent. The moisture permeability of the resulting PLA/PCL+OTOA films decreased due to the formation of uniformly distributed hydrophobic amorphous zones that prevents water penetration. This architecture affects the tensile characteristics of the films: strength decreases to 5.6 MPa, elastic modulus E by 40%. The behavior of film elasticity is associated with the redistribution of amorphous regions in the matrix. Additionally, PLA/PCL+OTOA films with 20, 30 and 40% of OTOA showed good antibacterial properties on Pseudomonas aeruginosa, Raoultella terrigena (Klebsiella terrigena) and Agrobacterium tumefaciens. Developed PLA/PCL+OTOA films could be used as packaging materials and wound dressings. By variation of the OTOA content, it is possible to tailor the physical-chemical and antibacterial properties of the developed films for various applications.