The Stoa of Zeus Eleftherios is located in the north-western part of the Ancient Agora, next to the Stoa Basileios (Royal Stoa). It was founded around 430-420 BCE and was dedicated to Zeus. Constructed on the site of an earlier sanctuary of Zeus Eleutherios, which was probably destroyed during the Persian Wars. In front of the Stoa, to the east, there was an Archaic altar dedicated to Zeus Eleutherios, whose worship was established after the wars against the Persians in the early 5th century BCE, when the Greeks were liberated from the Persian threat.

The Stoa is elongated, Doric in style, with two wings at the ends projecting to the east, giving the building a plan in the shape of the Greek letter “Π”. The crepidoma (platform upon which the superstructure of the building was erected) had three steps. Externally, the building had a Doric colonnade, which was denser along the wings giving the impression of a temple, while internally it had an Ionic colonnade. It was decorated with triglyphs (the vertically channelled tablets of the Doric frieze) and metopes (the square space between two triglyphs in a Doric frieze), and the roof had clay tiling and acroteria (ornamental sculptures). For the construction of the Stoa, Pentelic, Hymettian and marble from Aegina as well as limestone were used. The interior walls were decorated with paintings, including works of the famous painter Euphranor. In addition, shields of Athenians who had fallen in battle defending their homeland were dedicated to the Stoa in the 3rd century BCE.

Apart from its obvious religious character, the Stoa had a secular aspect. It was a place of culture, socialising and entertainment for the citizens, much like the Stoa Poikile. According to ancient sources, Socrates would meet his disciples and friends there, and it often hosted the philosopher Diogenes. Many scholars argue that the building also housed administrative services, being the seat of the six thesmothetai, officials with legal and judicial responsibilities. If this view is correct, it seems that the northwest side of the Agora would have been shaped as an administrative centre with the construction of the two Stoas, the Stoa of Eleftherios Zeus and the Stoa Basileios, which was the seat of the Archon Basileus (king magistrate).

During the early Roman period, two rooms were annexed to the western wall of the Stoa, for the formation of which extensive works were carried out on the rock of Agoraios Kolonos. These two rooms have been identified as places for the imperial worship of Augustus and possibly Rome.

The earlier view that the building was affected by the raid of the Heruli in 267 CE is not commonly accepted. Many scholars believe that the building stood in its place in the 4th century and suffered damages during the raid of Alaric in 496 CE. After its destruction, the deconstruction of its remnants began in order to reuse the architectural elements in other buildings.