AbstractSilicon (Si) is recognized as a promising anode material for next‐generation anodes due to its high capacity. However, large volume expansion and active particle pulverization during cycling rapidly deteriorate the battery performance. The relationship between Si anode particle size and particle pulverization, and the structure evolution of Si particles during cycling is not well understood. In this study, a quantitative, time‐resolved “operando” small angle X‐ray scattering (SAXS) investigation into the morphological change of unwrapped and reduced graphene oxide (rGO) wrapped Si nanoparticles (Si@rGO) is conducted with respect to the operating voltage. The results provide a clear picture of Si particle size change and the role of nonrigid rGO in mitigating Si volume expansion and pulverization. Further, this study demonstrates the advantage of “operando” SAXS in electrochemical environments as compared to other approaches.