Psychopathic aggressive behavior is extremely antisocial and its destructiveness can be appalling. Throughout the past and still at present, psychopathy has been the topic of descriptive, psychodynamic, genetic and biological investigations. This article addresses the question of whether psychopaths are free in their decisional capacity or whether their criminal acts are subjected to determinism. A brief review of the history of psychopathy, psychopathic aggressivity, and pertinent psychoanalytic views are presented, along with philosophical theories of free will and determinism. Recent findings of brain neuroimaging of psychopaths are discussed. Special regard is given to Libet’s theory of free will. The criminal responsibility of psychopaths is considered in view of free will and determinism.