Nanostructured multilayered coatings for metals are prepared to simultaneously provide a function of corrosion mitigation and of corrosion sensing for copper substrates. Silica nanocapsules, embedded in one layer of the coating, are used as a host for a corrosion inhibitor and as a sensor, which detect changes of pH value and release inhibitors via an optical signal. Furthermore, another layer in the coating exists in a nanonetwork loaded with another corrosion inhibitor, which is impregnated with a hydrophobic polymer. We demonstrate that a specific arrangement of layers leads to an optimum anticorrosion and sensing performance while the sensing signal can be prolonged for a long time. It is the first time that the fluorophore detecting corrosion is conjugated to the nanosensor and that nanofibers and nanocapsules are used simultaneously to load and release corrosion inhibitors for anticorrosion applications.