Prussian blue analogues (PBAs) have been proven as excellent Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) in acidic, neutral and alkaline media. Further improvements can be achieved by increasing their electrical conductivity, but scarce attention has been paid to quantify the electroactive sites of the electrocatalyst when this enhancement occurs. In this work, we have studied how the chemical design influences the specific density of electroactive sites in different Au–PBA nanostructures. Thus, we have first obtained and fully characterized a variety of monodisperse core@shell hybrid nanoparticles of Au@PBA (PBA of Ni^IIFe^II and Co^IIFe^II) with different shell sizes. Their catalytic activity is evaluated by studying the OER, which is compared to pristine PBAs and other Au–PBA heterostructures. By using the coulovoltammetric technique, we have demonstrated that the introduction of 5–10% of Au in weight in the core@shell leads to an increase in the electroactive mass and thus, to a higher density of active sites capable of taking part in the OER. This increase leads to a significant decrease in the onset potential (up to 100 mV) and an increase (up to 420%) in the current density recorded at an overpotential of 350 mV. However, the Tafel slope remains unchanged, suggesting that Au reduces the limiting potential of the catalyst with no variation in the reaction kinetics. These improvements are not observed in other Au–PBA nanostructures mainly due to a lower contact between both compounds and the Au oxidation. Hence, an Au core activates the PBA shell and increases the conductivity of the resulting hybrid, while the PBA shell prevents Au oxidation. The strong synergistic effect existing in the core@shell structure evidences the importance of the chemical design for preparing PBA-based nanostructures exhibiting better electrocatalytic performances and higher electrochemical stabilities.