Ferroelectric perovskites have recently attracted interest for a wide range of photocatalytic and electrochemical applications1 due to their intrinsic properties for light adsorption2, electron–hole pair separation3–5 and a hypothesized enhancement of catalytic activity by polarization switching6–8. However, most of the well-known ferroelectric perovskites e.g., BaTiO3 and Pb (Zr, Ti)O3 are known to have limited activity toward electrocatalytic reactions e.g. hydrogen evolution (HER) and water splitting.2 In this work, we demonstrate that introducing only a few mono layers of SrRuO3, a metallic oxide from perovskite family, can significantly enhance the catalytic activity of BaTiO3 toward HER. Using a combination of first principle DFT+U calculations and experiments on thin films grown by molecular beam epitaxy, we investigated the activity of heterostructures of different thicknesses toward HER in an alkaline electrolyte. Computational results show that the Gibbs free energy barrier of H* adsorption on one monolayer of SrRuO3 atop ferroelectric BaTiO3 is at least two times smaller than BaTiO3, depending on the adsorption site or the direction of ferroelectric polarization. In line with the findings from our DFT calculations, our experimental results confirm significantly higher current density and lower charge transfer resistance toward hydrogen evolution for SrRuO3/BaTiO3 heterostructures compared to bare BaTiO3 surfaces. Harnessing oxide heterostructures, as demonstrated here, opens the door to leveraging the unique properties of ferroelectrics as supports to promote electrocatalytic activity.