Methylaluminoxane (MAO) is commonly employed to activate molecular pre-catalysts in polyolefin synthesis, both industrially and in the laboratory. Despite the extensive use of this compound, the ambiguity related to its structure hampers the understanding of its structure-function relationship. The current study therefore employed synchrotron X-ray total scattering to elucidate the nano-sized molecular structure of MAO. The MAO samples, which were prepared using various synthetic protocols, exhibited consistent X-ray scattering patterns and atomic pair distribution function curves, indicating similar molecular structures. However, the scattering intensity in the small-angle region revealed differences in the higher-order structures. A fitting study performed using 172 molecular models showed that small molecule and tube models were inadequate to reproduce the experimental results, whereas cage and sheet models provided comparably better fits. The sheet model was found to be consistent with the observed molecular weight and the molecular weight distribution, in addition to accounting for the intensity in the small-angle scattering region. These results align with recent crystallographic findings reported in