The hierarchical Yen-Mullins model of Athabasca oil-sands asphaltene is strongly supported by solution-state H-1 NMR relaxation measurements and 2D HSQC-NMR spectroscopy. For the first time, the H-1 T-1 and T-2 relaxation behaviors of specific sites in asphaltene molecules have been studied, and it is shown that the relaxation behavior is in agreement with the hierarchical molecule-nanoaggregate-cluster model proposed by Mullins (Energy Fuels 2012, 26, 3986). The size of the asphaltene nanoaggregate clusters was determined from the biexponential T-2 relaxation behavior of the H-1 nuclei. Assignment of overlapping 1D NMR signals was made possible via HSQC methods, where elusive hallmark long-range aromatic-aliphatic heteronuclear correlations were observed. Alicyclic structures were shown to be more closely associated with the aromatic core than what has been proposed for most archipelago-type structures. The NMR parameters obtained from the deconvolution analysis indicate an average of 6-7 pericondensed aromatic rings present in each molecule, in agreement with the island model. The average molecular weight was determined at similar to 720 g/mol, which would be typical for island model structures, hence lending strong support for the Yen-Mullins model.