Multiferroic materials with coexisting ferroelectric and ferromagnetic orders have attracted much attention due to the magnetoelectric coupling opening alternative prospects for electronic devices. Composite multiferroics containing separate ferroelectric and ferromagnetic components are a promising alternative to the single‐phase counterparts. Composite multiferroic structures comprising HfO2‐based ferroelectrics are potentially feasible for technological applications. Here, this study reports on the experiments aiming at the manifestation of magnetoelectric coupling at Fe/Hf0.5Zr0.5O2 (HZO) interface. Using synchrotron based 57Fe Mössbauer spectroscopy technique in operando, this study probes element‐selectively the local magnetic properties of a nanometer‐thick enriched 57Fe marker layer in functional Pt/57Fe/HZO/TiN capacitors and demonstrates the evidence of the ferroelectric polarization effect on the …