In classical antiquity, the bouleuterion housed a council, the boule, which consisted of 500 Athenian citizens, who were in charge of the city's laws regarding the daily life. These citizens were chosen from among the ten Greek tribes, fifty from each, and they served for a year. From the ranks of the boule, one group of fifty was chosen every month to lead the executive committee, the prytaneis.
In 431 BCE, the Spartan misthios Kassandra visited the bouleuterion, witnessing the ostracization process of Anaxagoras, a philosopher and a friend of the statesman Perikles. There, she met Perikles' contact, who tasked her to swap a bag of votes at the nearby Logismos Building. After doing so, she returned to the contact and witnessed Anaxagoras being ostracized and was thus forced to leave Athens. Afterwards, she met the philosopher Sokrates, who introduced himself to her and was seemingly aware of her actions of fixing the vote.