The physical nature of the coke product of pyrolyzed heavy hydrocarbon fractions has been of great interest to the petroleum industry for the ease of its removal from the drum in delayed coking. The coking process itself and chemical makeup of the residuum feed have been studied to judge how the easily removed, granular shot coke can be preferentially formed over an immobilized sponge coke product. In this work, electron diffraction was employed to study the progression of molecular alignment in asphaltenes during the formation of their coke byproduct. Asphaltenes exhibit the same glassy molecular assembly revealed previously by X-ray diffraction, indicating that a 10(-9) sampled volume reduction betrays no increase of localized order. On the other hand, for cokes, the greatly reduced sampled volume reveals further structural details not detected in powder X-ray patterns, consistent with the ordering of "basic structural units" in early stages of graphitization. While the (002) stacking distance near 3.4 angstrom is commonly observed, variations of this spacing are somewhat insensitive to the early graphitization process, as are the lateral and stacked structural coherence. The most sensitive parameter for initial ordering appears to be the arcing of (002) reflections and the increasing number of its diffraction orders. The ordering seems to depend, in part, upon the time that the material is held at a higher temperature.