Previous neuroimaging studies have suggested that the neural bases of trait emotional intelligence (TEI) lie in the social cognition network (SCN) and the somatic marker circuitry (SMC). The current study was the first to investigate the associations of total TEI factors and subfactors with mean diffusivity (MD) of these networks as well as regional MD of the dopaminergic system (MDDS). We found that TEI intrapersonal factor score and total TEI score were negatively correlated with regional MDDS in the vicinity of the right putamen and right pallidum and that TEI intrapersonal factor score was negatively correlated with MD values of the fusiform gyrus. Total TEI score and TEI factor scores were positively correlated with MD values of various areas within or adjacent to SCN components, SMC structures and the lateral prefrontal cortex (LPFC). Our MD findings demonstrated the importance of the dopaminergic system to TEI and implicate the SCN, SMC and LPFC in TEI. Future studies are required to investigate the implications of positive and negative associations with MD values.