We investigate the dissociation mechanism of the C-N bond between carbazole and dibenzothiophene in carbazole-dibenzothiophene (Cz-DBT) positional isomers, selected as representative systems for blue host materials in organic light-emitting diodes (OLEDs). The C-N bond dissociation energies, calculated at the density functional theory level, are found to depend strongly on the charge states of the parental molecules. In particular, the anionic C-N bond dissociations resulting in a carbazole anion can have low dissociation energies (∼1.6 eV) with respect to blue emission energy. These low values are attributed to the large electron affinity of the carbazole radical, a feature that importantly can be modulated via substitution. Substitution also impacts the energies of the first excited electronic states of the Cz-DBT molecules since these states have an intramolecular charge-transfer nature due to the spatially localized character of the frontier molecular orbitals within the carbazole moiety (for the HOMO) and the dibenzothiophene moiety (for the LUMO). The implications of these results must be considered when designing blue OLED hosts since these materials must combine chemical stability and high triplet energy. © 2016 American Chemical Society.