An electrochemically generated alginate matrix cross-linked with Fe³⁺ cations was used to entrap lysozyme and then release it upon application of an electrochemical signal. The switchable behavior of the alginate hydrogel was based on the different interaction of Fe³⁺ and Fe²⁺ cations with alginate. The oxidized Fe³⁺ cations strongly interact with alginate resulting in its cross-linking and formation of the hydrogel, while the reduced Fe²⁺ cations weakly interact with alginate and do not keep it in the hydrogel state. Thus, the electrochemical oxidation of iron cations at +0.8 V (Ag/AgCl) in the presence of alginate and lysozyme resulted in the Fe³⁺-cross-linked alginate hydrogel thin-film on the electrode surface with the physically entrapped lysozyme. On the other hand, application of reductive potentials (e.g. −1.0 V) converted the iron cations to the Fe²⁺ state, thus resulting in dissolution of the alginate thin-film and lysozyme release. The bactericidal effect of the electrochemically released lysozyme was tested on the Gram-positive bacterium Micrococcus luteus demonstrating the same activity as the unadulterated lysozyme commercially supplied by Sigma-Aldrich. The present result represents the first step towards drug delivering systems (exemplified by the lysozyme release) based on alginate hydrogels and activated by electrochemical stimuli.