Final answer:
John Smith was presented before chief Powhatan at Werowocomoco, where Powhatan's daughter Pocahontas was also present. Neither John Rolfe nor Chief Opechancanough were present as per the narrative.
Step-by-step explanation:
When John Smith is brought to Werowocomoco, as described in The General History of Virginia, he is presented before the chief, Powhatan, who was seated as a king with attendants surrounding him. Among the crowd was Powhatan's daughter, Pocahontas, who played a noteworthy role in Smith's narrative. Neither John Rolfe nor Chief Opechancanough is mentioned to be present during this specific event. While Opechancanough did later become chief of the Powhatan and held John Smith captive at a different point, the correct answer to the question posed is A. Powhatan.