Nanostructures with stimuli‐responsive properties are of great importance for the application of smart materials in nanotechnology. Unique hollow polypyrrole nanostructured arrays with a conical shape have been produced by a stepwise electropolymerization process. The polypyrrole conical nanocontainers exhibit a reversible switchable behavior between open and closed states, which is controlled by the movement of counter ions during electrically controlled reversible oxidation and reduction processes. The formation of conical nanocontainers is affected by the oleo‐wettability of the substrate. Conical nanocontainers can be formed on oleo‐phobic substrates in aqueous solution by using dopant‐stabilized pyrrole nanodroplets as the guiding template for the polymerization.
