Despite numerous efforts, there are several fundamental ambiguities regarding the photoluminescence of carbon dots (CDs). Spectral shift measurements display characteristic of both π–π* and n–π* transitions for the main absorption or excitation band at ∼350 nm, contrary to common assignment of exclusive n–π* transition. Additionally, the generally perceived core-state transition at ∼250 nm, involving sp²-networked carbogenic domains shielded from external environments, needs to be reassessed because it fails to explain the observed fluorescence quenching and spectral shift. These results have been explained based on the molecular origin of PL in CDs invoking the similarity between CD and citrazinic acid. Fluorescent derivatives of the latter are recognized to be produced during citric-acid-based CD synthesis. Concentration-dependent spectral splitting of the main excitation band in combination with the temperature-dependent PL results has been envisioned assuming self-assembly of CDs into various H-aggregates.