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Aims: We investigated default mode network (DMN) electroencephalography (EEG) functional connectivity differences between individuals with self-reported high mentalization capability and low psychopathological symptoms, versus participants with mentalization impairments and high psychopathological symptoms. Methods: Forty-nine students (35 women) with a mean age of 22.92 ± 2.53 years were administered the Mentalization Questionnaire (MZQ) and the Symptom Checklist-90-Revised. Five minutes of EEG during resting state were also recorded for each participant. DMN functional connectivity analyses were conducted by means of the exact Low Resolution Electric Tomography software (eLORETA). Results: Compared to the individuals with high mentalization capability and lower self-reported psychopathological symptoms, participants with mentalization impairments and high psychopathological symptoms showed a decrease of EEG beta connectivity between: (i) the right and left medial frontal lobe, and (ii) the left medial frontal lobe and the right anterior cingulate cortex. Furthermore, while MZQ total score was positively associated with DMN network connections (i.e., right and left medial frontal lobes), several psychopathological symptoms (i.e., interpersonal sensitivity, depression, and psychoticism) were negatively associated with DMN connectivity. Conclusion: Our results may reflect a top-down emotion regulation deficit which is associated with both internalizing and externalizing behavior problems.