One prominent aggregation-related phenomenon is the fluorescence redshift when the concentration of asphaltene increases. However, the origin of this redshift is still under debate. Previous studies attributed it to nanoaggregate formation, experimental artifact of self-absorption, or intramolecular Förster resonance energy transfer (FRET). This controversy stems from the uncertainty of the structural fluorescence relationship of asphaltene aggregates. However, the obstacle of separating specific components from the asphaltene mixture hinders the experimental study of asphaltene aggregates. Therefore, theoretical modeling is needed to reveal the structure-fluorescence relationship of asphaltene aggregates.