Recently, so-called “nontraditional intrinsic luminescence” has been reported in several macromolecular systems. Although DABCO (1,4-diazabicyclo[2.2.2]octane) is the first system in which the effect was observed, a thorough analysis of the optical properties of the molecule, which would reveal the origin of this mysterious effect, is still pending. We perform an advanced post-Hartree–Fock treatment of the low-lying electronic states of this molecule, which need to be described with care because of their pronounced Rydberg character. We take a deeper look into the low-lying electronic transitions of DABCO targeting the explanation of the complex vibronic structures of its absorption and fluorescence spectra. Two electronic states, the 1E′(n+3pxy) and 1A2″(n+3pz) states, contribute to the absorption spectrum in the 39000–46000 cm–1 spectral range. We also reveal the spectroscopic signature of the 1A2″(n+3pz) state. The analyses of the contributions of individual vibrational normal modes allowed the identification of those giving rise to the complex vibronic structures of the spectra. Fluorescence emission arises from the vibronic coupling of the one-photon forbidden transition between the 1A1′(n+3s) state and the electronic ground state. The spectrum, which can be interpreted in terms of populating a few vibrational normal modes, is shifted toward visible wavelengths mostly due to the forced interaction of the lone pair electrons of the two nitrogen atoms. Our work on DABCO may help to rationalize the luminescence of more complex systems containing tertiary amine groups.