First ultrafast MAS solid-state 1H NMR study of asphaltenes. High spin-rate allows detection of otherwise obscure signals. Double Quantum correlation and T2 relaxation experiments help elucidate asphaltene aggregate structure. Asphaltenes mostly consist of large single-core PAHs. Nanoaggregation occurs through π-π interactions, and clusters consist of a rigid central core and a mobile periphery.