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Jack Bauer is now at the Okavango school in Sangala, a fictional African country, helping his old friend Carl Benton (Robert Carlyle) with missionary work, attempting to find peace. He has been served a subpoena to appear before the U.S. Senate regarding torture charges, but refuses to go. A U.S. State Department official, Frank Trammel, hints that the Embassy will cut funding for Benton's school if Benton continues to protect Jack, so Jack decides to leave. Meanwhile, two boys from the school are playing soccer with some other boys at a field in town when they are ambushed by soldiers in General Juma's militia, intending to recruit them as soldiers for Juma's coup d'etat, which Juma is planning and arming with aid from a secret organisation within the U.S. government. The two boys run, but are shot, leaving one dead and the other wounded.

Benton drives to town to investigate the missing children, and soon finds the two boys. He calls Jack, who is leaving, telling him that Juma's men are heading for the school. Jack hides the children in an underground shelter and then arms himself from Benton's weapons cache. As the soldiers arrive, Jack ambushes them and kills several men before getting captured. The rebels torture Jack to obtain the location of the hidden children, but Jack instead sends them into the bush, where Benton has returned and is waiting. Benton ambushes the remaining three soldiers, while Jack kills the leader, the brother of Ike Dubaku, a high-ranking rebel commander. Ike soon learns of his brother's death and plots revenge, while Jack and Benton decide to drive the children to the U.S. Embassy in the capital city to evacuate them. However, they only have until 5 PM, when the last helicopter will leave. On the way, rebel patrols force them to abandon their bus and travel the remainder of the journey on foot.

In Washington DC, Chris Whitley (Kris Lemche) is ordered by the conspirators to erase all information that would incriminate them. Instead, he decides to call his friend Roger Taylor (Eric Lively), the son of President-elect Allison Taylor, who is only hours away from being sworn in. Whitley meets Roger and tells him about the possible conspiracy. Roger reluctantly agrees to help, but when Whitley returns home to retrieve the data he was instructed to erase, he is stopped by men who work for Jonas Hodges (Jon Voight), one of the conspirators. The men take the information and kill Whitley, burying him in concrete to hide the body.

Jack, Benton, and the children are walking along a river when they are spotted by Ike's helicopter, and take cover in the forest. Ike and his men follow them on foot and are gaining ground on them when Benton accidentally steps on a land mine. Jack tries to disarm it, but with little time Benton begs him to leave so he can buy time. Jack reluctantly leaves with the children. Benton waits until he is surrounded by Ike and his men before taking his foot off the trigger, detonating the mine and killing himself as well as the rebels. However, Ike himself survives, wounded (as revealed in the extended edition). Jack and the children continue to the capital, where everyone is fleeing to the embassy. As Jack and the children approach, they are ambushed by several rebels, whom Jack is able to defeat. He then encounters the boy who was brainwashed in the prologue, and manages to convince him to put down his rifle. With minutes to go Jack reaches the embassy with the children. However since Benton (their legal guardian) is dead, Trammel is able to blackmail Jack into surrendering himself in order to guarantee the children's safety. Meanwhile in Washington D.C, Allison Taylor is inaugurated as President of the United States. Jack is arrested and leaves with the children by helicopter, as hundreds of Sangalans are left behind outside the embassy gates.