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In a combined experimental and theoretical study we assess the role of Co incorporation on the OER activity of LaCoxFe1 xO3. Phase pure perovskites were synthesized up to x 0.300 in 0.025 0.050 steps. HAADF STEM and EDX analysis points towards FeO2 terminated 001 facets in LaFeO3, in accordance with the stability diagram obtained from density functional theory calculations with a Hubbard U term DFT U . Linear sweep voltammetry conducted in a rotating disk electrode setup shows a reduction of the OER overpotential and a nonmonotonic trend with x, with double layer capacitance measurements indicating an intrinsic nature of activity. This is supported by DFT U results that show reduced overpotentials for both Fe and Co reaction sites with the latter reaching values of 0.32 0.40 V, 0.3 V lower than for Fe. This correlates with a stronger reduction of the binding energy difference of the O and OH intermediates towards an optimum value of 1.6 eV for x 0.250, the OH deprotonation being the potential limiting step in most cases. Significant variations of the magnetic moments of both surface and subsurface Co and Fe during OER demonstrate that the beneficial effect is a result of a concerted action involving many surrounding ions, which extends the concept of the active site