This work provides a concrete example on the limits of the core-shell model and how advanced, albeit computationally demanding, techniques can provide a way to obtain reliable interpretation of complex data and the prediction of unexpected, novel structures. The structure of Triton X-100 assemblies is examined and compared with that of C12EO10 micelles. Although both have similar molecular weights and identical hydrophilic segments, our findings reveal that Triton X-100 cannot be represented by a singular structure. Instead, it exhibits an ensemble of structures including non-core-shell formations.