AbstractThe Invar effect is universally observed in Fe-based bulk metallic glasses. However, there is limited understanding on how this effect manifests at the atomic scale. Here, we use in-situ synchrotron-based high-energy X-ray diffraction to study the structural transformations of (Fe_71.2B₂₄Y_4.8)₉₆Nb₄ and (Fe_73.2B₂₂Y_4.8)₉₅Mo₅ bulk metallic glasses around the Curie temperature to understand the Invar effect they exhibit. The first two diffraction peaks shift in accordance with the macroscopically measured thermal expansion, which reveals the Invar effect. Additionally, the nearest-neighbor Fe–Fe pair distance correlates well with the macroscopic thermal expansion. In-situ X-ray diffraction is thus able to elucidate the Invar effect in Fe-based metallic glasses at the atomic scale. Here, we find that the Invar effect is not just a macroscopic effect but has a clear atomistic equivalent in the average Fe–Fe pair distance and also shows itself in higher-order atomic shells composed of multiple atom species.