Very little is known on white-collar crime and how it differs to other forms of offending. This study tests the hypothesis that white-collar criminals have better executive functioning, enhanced information processing, and structural brain superiorities compared with offender controls. Using a case-control design, executive functioning, orienting, and cortical thickness was assessed in 21 white-collar criminals matched with 21 controls on age, gender, ethnicity, and general level of criminal offending. White-collar criminals had significantly better executive functioning, increased electrodermal orienting, increased arousal, and increased cortical gray matter thickness in the ventromedial prefrontal cortex, inferior frontal gyrus, somatosensory cortex, and the temporal-parietal junction compared with controls. Results, while initial, constitute the first findings on neurobiological characteristics of white-collar criminals. It is hypothesized that white-collar criminals have information-processing and brain superiorities that give them an advantage in perpetrating criminal offenses in occupational settings. Hum Brain Mapp, 2012. © 2011 Wiley Periodicals, Inc.