We demonstrate here that the control over the release rate of payloads and on the selectivity of the release can be achieved by designing nanomaterials with a hierarchical structure. Redox-responsive silica nanocapsules are first synthesized to allow for an accelerated release of the corrosion inhibitor 2-mercapto-benzothiazole as a payload upon chemical reduction and retarded release upon oxidation. In a second step, we embedded the nanocapsules into nanofibers by colloid-electrospinning, yielding a hierarchical composite structure. Remarkably, the encapsulation of the nanocapsules in the fibers provides two decisive advantages that are a higher selectivity of the release and a higher control over the release rate of payloads.