The current study explored how hot and cool executive functions (EF) could predict resting-state connectivity of the Default Mode Network (DMN) and Central Executive Network (CEN) in a mixed clinical and typically developing sample of adolescents. It was hypothesized that hot EF would predict a quadratic, inverted U-shaped, relationship between connectivity of the major regions of the DMN: the Posterior Cingulate Cortex (PCC) and the Medial Prefrontal Cortex (MPFC). It also was hypothesized that cool EF would predict a quadratic, inverted U-shaped, relationship between the connectivity of the major regions of the CEN: the right Posterior Parietal Cortex (right PPC) and the right Dorsal Lateral Prefrontal Cortex (right DLPFC). The results suggested that hot EF, specifically emotional regulation, predicted a quadratic relationship in DMN connectivity. However, this relationship was U-shaped instead of an inverted U-shaped. Thus, participants who scored well or poorly in emotional regulation generally had higher connectivity than those with average scores in emotional regulation. There were no significant results between cool EF and the CEN. Additional exploratory analysis suggested that the main hypotheses were not driven or suppressed by group differences. Further exploration observed other brain regions involved in resting-state activity that may play a role in hot or cool EF. Overall, findings support the Internal Mentation Hypothesis of DMN activity and are indicative of a relationship between emotional regulation and DMN resting-state connectivity.