In this work, we utilized the extended Frenkel exciton model to investigate the influence of monomer properties and intermolecular conformation on asphaltene dimer fluorescence via TDDFT calculations. We utilized monomers from real asphaltene systems obtained from STM and AFM imaging and formed a data set of 496 asphaltene dimers to obtain data-driven insights. Our results show that the fluorescence energy of asphaltene dimers never exceeds its lowest monomer fluorescence energy, with its further redshift mainly caused by the superexchange effect. This work provides important theoretical support for understanding the relationship between asphaltene aggregation and the variation in its fluorescence spectrum.