Asphaltenes are polydisperse, compositionally complex solubility fractions of crude oil, with a range of structural motifs that contain two primary structural classes: molecules with single aromatic cores (island) and bridged aromatic moieties (archipelago), each with varying degrees of alkyl substitution (e.g., varied-length alkyl units) and multi-heteroatom functionalities responsible for aggregate formation through weak and strong intermolecular associations. Understanding the link between asphaltene molecular composition and problematic behavior, such as deposit and emulsion formation, is vital to improve crude oils up- and downstream processes in petrochemical industries. Some reports suggest that asphaltene precipitation occurs primarily through self-association of polar functional groups and highlight direct correlations between aggregate size and emulsion stability. Here, we compare the molecular composition of whole and thin-layer chromatography (TLC)-fractioned PetroPhase 2017 asphaltenes characterized by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and correlate composition to near-infrared (NIR) scattering measurements of heptane/toluene (HepTol) dispersions. Asphaltene retention on SiO2 plates is dictated by molecular features, such as aromaticity, heteroatom content, and degree of saturation (or content of methylene units). The most polar molecules in PetroPhase 2017 asphaltenes are strongly retained on SiO2 and exhibit a bimodal distribution in compositional space (carbon number and aromaticity) characterized by highly alkylated and highly heteroatomic (N, O, and S) species. In contrast, the least retained compounds consist of primarily highly aromatic, sulfur containing species with short alkyl chains. Furthermore, a correlation between asphaltene aggregation and emulsion stability was observed: for the fraction that was retained the most on the silica plate, the quicker it aggregates in HepTol and the more stable its emulsion. Collectively, this suggests that not all asphaltenes are the same and indicates the presence of a direct relationship between asphaltene polarity, aggregation tendency, and emulsion stability.