Research suggests that emotional intelligence capacities may be related to the functional integrity of the corticolimbic regions including the ventromedial prefrontal cortex, insula, and amygdala. No study has yet examined regional brain volumes in relation to the two dominant models of emotional intelligence: the Ability model, which posits a set of specific demonstrable capabilities for solving emotional problems, and the Trait model, which proposes a set of stable emotional competencies that can be assessed through subjectively rated self-report scales. In 36 healthy participants, we correlated scores on the Mayer-Salovey-Caruso Emotional Intelligence Test (an Ability measure) and the Bar-On Emotional Quotient Inventory (a Trait measure) with regional brain volumes using voxel-based morphometry. Total Mayer-Salovey-Caruso Emotional Intelligence Test scores were positively correlated with the left insula grey matter volume. The Strategic emotional intelligence subscale correlated positively with the left ventromedial prefrontal cortex and insular volume. In contrast, for the Bar-On Emotional Quotient Inventory, Stress Management scores correlated positively with the bilateral ventromedial prefrontal cortex volume. Amygdala volumes were unrelated to emotional intelligence measures. Findings support the role of the ventromedial prefrontal cortex and insula as key nodes in the emotional intelligence circuitry.