In this work, we show how the activity states of bimetallic Ni0-Fe0 catalysts exsolved from Nd0.6Ca0.4Fe0.97Ni0.03O3−δ (NCFNi) can be influenced electrochemically. The NCFNi parent oxide was employed in the form of thin film mixed conducting model electrodes, which were operated in a humid hydrogen atmosphere. By precisely controlling the oxygen chemical potential in the parent oxide electrode via applying an electrochemical polarisation, we managed to selectively exsolve Ni nanoparticles from the perovskite lattice and study their catalytic activity switching characteristics. To be able to track the surface chemical changes during the switching process, electrochemical polarisation experiments were combined with near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) measurements. This in situ analytical approach allowed relating the difference we observed in the switching behaviour of Ni particles here and of Fe particles in a recent study, to a different kinetic interplay between electrochemical driving force and atmosphere. We propose that slow oxygen transport through nickel oxide, located at the particle/perovskite interface, is mainly responsible for the observed difference to iron exsolutions, which becomes especially evident for larger nickel particles. In addition, in the case of bimetallic exsolutions and with applied bias voltage as a control parameter, we are able to reversibly switch between three different activity states, namely bimetallic Ni0-Fe0 (medium activity), pure Ni0 (high activity), and the inactive oxides.