Based on Ron Hansen's 1983 novel of the same name, director Andrew Dominik and his creative team made a lavish film chronicling the life of two men. These two men are Jesse James, known in some cases as the Dark Angel and the Robin Hood of the west, and Robert Ford, the mousy coward who killed him. This film chooses to examine these two men psychologically rather than re-tell the flamboyant tales originating from the dime novels of the 1870s and persisting to the present-day myths.

The film opens with the late night Blue Cut train robbery when the James Gang was in their outlaw prime. The real drama unfolds in the robbery's aftermath, when these gang members compete for Jesse's attention. Jesse's (Brad Pitt) personal demons, such as being somewhat schizophrenic and intensely paranoid, had the members of the gang on edge and anxious. Their attention was centered on him, causing the gang to struggle with themselves and cater to his desires. They do not connect with each other.

This examination of human behavior, ego, and resentment is the theme of this intriguing film. When Robert Ford (Casey Affleck) met Jesse and showed his admiration for him, Jesse welcomed it. The young, insecure Robert Ford collected and read the dime novels written about his hero (Jesse) and worshipped him. Charlie Ford (Sam Rockwell) had been a member of the gang, so Jesse decided to recruit young Robert. Between train and bank robberies Jesse, now known as Thomas Howard, kept Robert around as a houseguest if only to stroke his ego and run errands. All the time, Robert was gaining Jesse's confidence.

The film shows the life and death situations Jesse would put himself into as if he enjoyed it. This was his way of living on the edge, all the while having the other members of his gang feeling uneasy and questioning his reasoning. He threatened and killed members he felt would benefit from turning him in. Brad Pitt's performance in displaying the mood swings in his character was mesmerizing. It seemed that Jesse just wanted the sensational feeling of knowing that death was a possibility in the last years of his life. With Robert Ford sharing his home, he was setting himself up to be killed or captured.