Oxygen‐depolarized cathodes (ODC) were developed for chlor‐alkali electrolysis to replace the hydrogen evolution reaction (HER) by the oxygen reduction reaction (ORR) providing electrical energy savings up to 30 % under industrially relevant conditions. These electrodes consist of micro sized silver grains and polytetrafluoroethylene, forming a homogeneous electrode structure. In this work, we report on the modification of ODCs by implementing an electrospun layer of hydrophobic poly(vinylidene

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... fluoride) (PVDF) into the ODC structure, leading to a significantly enhanced ORR performance. The modified electrodes are physically characterized by liquid flow porometry, contact angle measurements and scanning electron microscopy. Electrochemical characterization is performed by linear sweep voltammetry and chronopotentiometry. The overpotential for ORR at application near conditions could be reduced by up to 75 mV at 4 kA m−2 and 135 mV at a higher current density of 9.5 kA m−2. Consequently, we propose that modifying ODCs by electrospinning is an effective and cost‐efficient way to further reduce the energy demand of the ORR in highly alkaline media.