Multilayer composites that utilize polymeric and brittle inorganic films are essential components for extending the lifetimes and exploiting the flexibility of many electronic devices. However, crack formation within the brittle inorganic layers that arise from defects as well as the flexing of these multilayer composite materials allows the influx of atmospheric water, a major source of device degradation. Thus, a composite material that can initiate self-healing upon the influx of environmental water through defects or stress-induced cracks would find potential applications in multilayer composite materials for permeation barriers. In the present study, the reactive metal oxide precursor TiCl4 is encapsulated within the pores of a degradable polymer, poly(lactic acid) (PLA). Electrospun PLA fibers are found to be reactive to atmospheric water leading to the hydrolysis of the degradable polymer shell and subsequent release of the reactive metal oxide precursor. Release of the reactive TiCl4 from the pores results in hydrolysis of the metal oxide precursor, forming solid titanium oxides at the surface of the fibers. The efficacy of this self-healing delivery system is also demonstrated by the integration of these reactive fibers in the polymer planarization layer, poly(methyl methacrylate), of a multilayer film, upon which an alumina barrier layer is deposited. The introduction of nanocracks in the alumina barrier layer lead to the release of the metal oxide precursor from the pores of the fibers and the formation of titanium dioxide nanoparticles within the crack and upon the thin film surface. In this study the first delivery system that may find utility for the self-healing of multilayer barrier films through the site-specific delivery of metal oxide nanoparticles through smart reactive composite fibers is established.