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A metal–organic framework (MOF), ZIF‐8, which is stable at neutral and slightly basic pH values in aqueous solutions and destabilized/dissolved under acidic conditions, is loaded with a pH‐insensitive fluorescent dye, rhodamine‐B isothiocyanate, as a model payload species. Then, the MOF species are immobilized at an electrode surface. The local (interfacial) pH value is rapidly decreased by means of an electrochemically stimulated ascorbate oxidation at +0.4 V (Ag/AgCl/KCl). Oxygen reduction upon switching the applied potential to −0.8 V allows to return the local pH to the neutral/basic pH, then stopping rapidly the release process. The developed method allows electrochemical control over stimulated or inhibited payload release processes from the MOF. The pH variation proceeds in a thin film of the solution near the electrode surface. The switchable release process is realized in a buffer solution and …