X-ray absorption and small-angle x-ray scattering spectra were simultaneously acquired under operando conditions in a joined technique approach, for the first time applied in the field of energy storage materials. This approach allows one to closely follow the electronic and local structure evolution, as well as monitor and quantify the morphological and nanostructural changes occurring during electrochemical cycling. Here we demonstrate its potential on the example of doped and non-doped Fe₂O₃ anode material vs. Li. Our results reveal that upon discharge Fe³⁺ is gradually reduced to the metallic state and segregated as nanoparticles. For the relithiation reaction, upon subsequent charge, we observe improved reversibility for the Sr-doped compared to non-doped and Ca-doped Fe₂O₃. We highlight that this combined technique approach is a reliable, facile and powerful tool to investigate electrode materials under realistic cycling condition. It provides an unbiased and holistic picture of the morphological and structural changes occurring during operation, which allows for adequate material tailoring.