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Simultaneous electroreduction of CO 2 and H 2 O to syngas can provide a sustainable feed for established processes used to synthesize carbon-based chemicals. The synthesis of MO x /M-N-Cs (M = Ni, Fe) electrocatalysts reported via one-step pyrolysis that shows increased performance during syngas electrosynthesis at high current densities with adaptable H 2 /CO ratios, e.g., for the Fischer-Tropsch process. When embedded in gas diffusion electrodes (GDEs) with optimized hydrophobicity, the NiO x /Ni-N-C catalyst produces syngas (H 2 /CO = 0.67) at -200 mA cm -2 while for the FeO x /Fe-N-C syngas production occurs at ≈-150 mA cm -2 . By tuning the electrocatalyst's microenvironment, stable operation for >3 h at -200 mA cm -2 is achieved with the NiO x /Ni-N-C GDE. Post-electrolysis characterization revealed that the restructuring of the catalyst via reduction of NiO x to metallic Ni NPs still enables stable operation of the electrode at -200 mA cm -2 , when embedded in an optimized microenvironment. The ionomer and additives used in the catalyst layer are important for the observed stable operation. Operando Raman measurements confirm the presence of NiO x during CO formation and indicate weak adsorption of CO on the catalyst surface., (© 2024 The Authors. Small published by Wiley‐VCH GmbH.)