Bimetallic nanoparticles are widely studied, for example in catalysis. However, possible restructuring in the environment of use, such as segregation or alloying, may occur. Taken individually, state‐of‐the‐art analytical tools fail to give an overall picture of these transformations. This study combines an ensemble analysis (near‐ambient‐pressure X‐ray photoelectron spectroscopy) with a local analysis (environmental transmission electron microscopy) to provide an in situ description of the restructuring of core–shell nickel‐cobalt nanoparticles exposed to cycles of reduction and oxidation. It reveals a partial surface alloying accompanied by fragmentation of the shell into smaller clusters, which is not reversible. Beyond this case study, the methodology proposed here should be applicable in a broad range of studies dealing with the reactivity of mono‐ or bi‐metallic metal nanoparticles.