Here it is demonstrated that multiple-energy, anomalous small-angle X-ray scattering (ASAXS) provides significant enhancement in sensitivity to internal material boundaries of layered nanoparticles compared with the traditional modeling of a single scattering energy, even for cases in which high scattering contrast naturally exists. Specifically, the material-specific structure of monodispersed Fe3O4 vertical bar gamma-Mn2O3 core vertical bar shell nanoparticles is determined, and the contribution of each component to the total scattering profile is identified with unprecedented clarity. We show that Fe3O4 vertical bar gamma-Mn2O3 core vertical bar shell nanoparticles with a diameter of 8.2 +/- 0.2 nm consist of a core with a composition near Fe3O4 surrounded by a (MnxFe1-x)(3)O-4 shell with a graded composition, ranging from x approximate to 0.40 at the Inner shell toward x approximate to 0.46 at the surface. Evaluation of the scattering contribution arising from the interference between material-specific layers additionally reveals the presence of Fe3O4 cores without a coating shell. Finally, it is found that the material-specific scattering profile shapes and chemical compositions extracted by this method are independent of the original input chemical compositions used in the analysis, revealing multiple-energy ASAXS as a powerful tool for determining internal nanostructured morphology even if the exact composition of the individual layers is not known a priori.