Relative to the general population, individuals with psychotic disorders have a higher risk of suicide. Suicide risk is also elevated in criminal offenders. Thus, psychotic-disordered individuals with antisocial tendencies may form an especially high-risk group. We built upon prior risk analyses by examining whether neurobehavioral correlates of social cognition were associated with suicidal behavior in criminal offenders with psychotic disorders. We assessed empathic accuracy and brain structure in four groups: (i) incarcerated offenders with psychotic disorders and past suicide attempts, (ii) incarcerated offenders with psychotic disorders and no suicide attempts, (iii) incarcerated offenders without psychotic disorders and (iv) community non-offenders without psychotic disorders. Established suicide risk variables were examined along with empathic accuracy and gray matter in brain regions implicated in social cognition. Relative to the other groups, offenders with psychotic disorders and suicide attempts had lower empathic accuracy and smaller temporal pole volumes. Empathic accuracy and temporal pole volumes were significantly associated with suicide attempts independent of other risk variables. The results indicate that brain and behavioral correlates of social cognition may add incremental value to models of suicide risk.