John Rolfe is a dashing young English diplomat in service to King James. He is sent to Jamestown with the task of bringing Chief Powhatan back to England for negotiations in order to prevent a war between the natives and the English. His character is based on the historical John Rolfe, who was married to the real life Pocahontas. In the film, he and Pocahontas are initially at odds, but he eventually falls strongly in love with her.
John Rolfe is known for his need to be in charge, which annoys Pocahontas at first. He shows much class and good manners during the voyage back to England when he guards Pocahontas from the rough crew, thus earning her respect.
John Rolfe is tasked by King James with bringing Chief Powhatan to London for negotiations in order to avoid another war between the natives and the settlers. He is greeted by the settlers in Jamestown, as well as Pocahontas. However, he dislikes Pocahontas initially when she rebukes him for interfering with an incident between Powhatan warriors and the settlers, who were about to attack one another.
Later, Rolfe overhears two women talking about how Pocahontas stopped a war, and falsely assumes that Pocahontas is the name of the chief, rather than of the young woman he just met. That night, he brings a horse as a gift for the "chief" but is astonished to learn who Pocahontas really is. The real chief, Powhatan, refuses to go to England, and so Rolfe is forced to take Pocahontas so that war can be avoided. Rolfe and Pocahontas clash on the voyage, but soon reach a truce after Rolfe saves Pocahontas from being arrested for keeping stowaways (Flit, Meeko, and Percy) on the ship.
In England, Rolfe is given a proclamation by Governor Ratcliffe on behalf of the king, which states that if King James is not impressed by the Powhatan ambassador, an armada will set sail for Jamestown. After resting at his estate, Rolfe meets with King James. At Ratcliffe's suggestion, both Rolfe and Pocahontas are invited to a ball that night. Pocahontas would have to impress the king by appearing "civilized" in order to prevent the armada from sailing, much to the disgust of John Rolfe.
Pocahontas AGREES to the plan, despite Rolfe's doubts, and is tutored in dancing and etiquette. Pocahontas dons a dress, and is powdered white, and is able to impress the king at first. However, Pocahontas offends the king by protesting a bear-baiting, which results in her being arrested and Rolfe's hopes for peace being shattered. That night, Rolfe meets a hooded stranger who assists him in breaking Pocahontas out of prison. At a cabin, the stranger reveals himself to be John Smith, who had been assumed dead after Ratcliffe had tried to arrest him. The fact that John Smith is still alive proves that Ratcliffe had been lying to the king in order to avoid his own crimes. While John Smith wishes for Pocahontas to remain hidden, John Rolfe allows Pocahontas to follow her heart. Smith soon realizes that Rolfe loves her.
Pocahontas goes before the king and queen, and, with the help of John Smith and John Rolfe, is able to reveal Ratcliffe as a traitor and liar. John Rolfe and the others then race to stop the armada, which they do so successfully. For his part in revealing the plot, Rolfe is offered a position as the king's adviser. He chooses to stay and Pocahontas chooses to head home alone. On the ship, Rolfe suddenly appears, revealing that he has actually turned down the king's position in favor of staying with her. John Rolfe and Pocahontas passionately embrace and romantically kiss as the ship sails off in the sunset.