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In the back woods of Harlan County, Tennessee, Korean war veteran and moonshine runner Lucas Doolin evades arrest by agents of the Alcohol, Tobacco and Treasury Department, led by Troy Barrett. Upon returning to his home in a country valley, Luke has his younger brother Robin repair the damage done to his car during the escape. A little later, neighbor Roxanna "Roxie" Ledbetter stops at the Doolins' to invite Luke to an upcoming dance, but Luke declines, as he will be on another delivery run. The next day, Roxie telephones the Doolins to report that a local liquor transporter was killed in an ambush. When Luke relays the news to his father Vernon, the older man suspects that the ambush was set up by racketeer Carl Kogan, who controls most of the moonshine counties in Tennessee and Kentucky and has proposed to organize Harlan County. Luke rejects Kogan's demand for a percentage of their profits and control over their operation. Later, after Luke departs on another delivery, a church service is held for the ambushed driver while a meeting of the county moonshiners is held in the church basement. Vernon recommends that all the stiller and transporters in the county be contacted and their stills be relocated, and that the transport cars and routes be changed to avoid Kogan's encroachment. Vernon adds that Luke has suggested all drivers carry shotguns for self-defense. With the exception of young Stacey Gouge and retired Jess, the county moonshiners vote to reject Kogan's proposal. The night of the dance, Robin asks to accompany Luke on his liquor delivery, but Luke refuses, telling his brother that he will never allow him in the "business." En route to Memphis, Luke is shot at on a back road and then followed by a pair of Kogan's men. Using a device that Robin has attached to the car, Luke sprays the road behind him with oil, causing Kogan's men to lose control of their car and crash. Outside of Memphis, Luke stops at Frank's garage to deliver his 250 gallon load of liquor. Later, Luke visits a Memphis nightclub to see his girl friend, singer Francie Wymore. When Kogan's crony Lucky presses Luke to meet with Kogan, Luke refuses. The next day, however, Luke stops at a garage that Kogan owns, and to his surprise, finds Stacey working there. Luke meets with Kogan privately and rebuffs his blunt offer to join him. When Kogan then threatens him, Luke knocks him out and escapes through the window. Two patrolmen report Luke's escape to Barrett who orders him taken into custody. Although Luke gives the police an alias, Barrett tells him that he knows his identity as a longtime whiskey runner and asks him for help in identifying the racketeer trying to break into the area. Even though Luke refuses, Barrett authorizes his release, anticipating that Luke will eventually lead him to Kogan. Luke returns to visit Francie, where he reflects on why he is considered an outlaw when he is only continuing his family's long tradition of moonshining. Luke then notes the irony of being pursued by the government that he served during the war. Francie asks Luke to give up his deliveries and settle down with her, but despite his feelings for her, Luke confesses that he is a loner. Later, Luke returns home in a new car that Robin promptly fits with a tanker. When fellow transporter Jed Moultrie asks to buy Luke's old car, Luke attempts to dissuade him, pointing out that the car is too well-known. Jed insists, however and Luke eventually agrees. Meanwhile, suspicious that Luke's hasty release from jail indicates he is helping the police, Kogan orders Lucky to kill him. A few days later in town, Barrett and his partner, Mike Williams, spot Luke's car and as Williams questions Jed, the car explodes, killing both men. Although Luke feels guilty about Jed's death, he refuses to stop his deliveries, but assures both Roxie and his mother Sarah that he will never allow Robin to become involved. Soon after the explosion, Barrett and his men arrest many moonshiners and destroy numerous stills. Barrett's arrests and Kogan's threats put pressure on the moonshiners, prompting them to close their stills. Vernon confesses to Jess that after his last supply of whiskey is delivered, he will close down as well, but remains certain that moonshining will return to the valley someday. While taking Vernon's last delivery to Memphis, Luke is ambushed by Lucky, but succeeds in crashing through his car barrier. Stopping at Frank's for repairs, Luke phones Vernon to assure him that he is safe. Meanwhile, Barrett stops at the Doolins' and asks Robin where he can find Luke. Although Robin refuses to cooperate with Barrett, the agent asks him to warn Luke that Kogan is determined to kill him and that Barrett needs Luke's help to arrest Kogan. Learning of Luke's whereabouts from Vernon, Robin takes a bus to warn Luke, but his brother refuses to meet with Barrett. Angered when Luke refuses to take him along, Robin returns home and accepts an offer to make a whiskey delivery for Stacey, unaware that he is working for Kogan. Roxie learns of Robin's plans and locates Luke in time for him to stop the delivery. Luke sends Robin home, then telephones Kogan and threatens to kill him for daring to involve Robin in his plans. Concerned when Robin returns home without Luke, Roxie looks for Barrett and is assisted by his wife Mary. While Luke meets Francie at a roadside cafe, Barrett arrests Kogan for involvement in Williams' and Jed's murders. Barrett then orders roadblocks erected to intercept Luke, who has resumed his Memphis delivery. Traveling at high speed, Luke's car runs over a barricade, spins out of control and crashes into an electrical power building, killing Luke. Witnessing the accident's aftermath, Barrett laments Luke's death. Back in the valley, Roxie and Robin wait together while Luke's body is brought home.