The influence of electrical polarization on Mn in La0.5Sr0.5MnO3±δ electrodes has been investigated by operando High Energy Resolved Fluorescence Detected X-Ray Absorption Near-Edge Structure (HERFD-XANES) spectroscopy, Kβ X-ray Emission Spectroscopy (XES) and Resonant Inelastic X-ray Scattering (RIXS) at the Mn K-edge. The study of polarization induced changes in the electronic properties and structure has been carried out at 500°C in 10–20% O2 with electrical polarization applied in the range from −850 mV to 800 mV. Cathodic polarizations in the range −600 mV to −850 mV induced a shift in the Mn K edge energy towards lower energies. The shift is assigned to a decrease in the average Mn oxidation state, which based on Kβ XES changes from 3.4 at open circuit voltage to 3.2 at −800 mV applied potential. Furthermore, RIXS rendered pronounced changes in the population of the Mn 3d orbitals, due to filling of the Mn d-orbitals during the cathodic polarization. Overall, the study experimentally links the electrical polarization of LSM electrodes to the structural and electronic properties of Mn - these properties are expected to be of major importance for the electrocatalytic performance of LSM electrode towards the oxygen reduction reaction.