The presence of humans at the current borders of the prefecture of Arta during the Palaeolithic age has not been determined with certainty and is limited to an unconfirmed information about the existence of Palaeolithic tools near the village of Grammenitsa. Equally few are also the discoveries that are dated at the Neolithic age and are represented by a stone axe part, which was located south of the ancient citadel of Ammotopos (ancient Orraon). In the same place very few shells of vessels dated at the age of Copper were also found. During the 9th century B.C. the region near the coast was inhabited, according the ancient literature sources, by Dryopes, a Thesprotian tribe, while the mountainous north-eastern department was part of the territory of Amfilohon people and potentially of Athamanon people, from Athamanika mountains (today's Tzoumerka) took their name. In the northern regions lived the Mollossoi, an important continental tribe.
One century later, Corinthian settlers made their first commercial installation (probably a small settlement) at the place that later Amvrakia was founded. The relations of Korinthian settlers with the native residents of Epirus, is reflected to the known myth of Gerioni's oxen seizing by Hercules. According to the Ekteos, Gerioni was king of the country near Amvrakia and owned the infamous oxen, which were seized by Hercules. The ancient tradition also reports that the possession of Amvrakia was claimed by Apollo, Artemis and Hercules, who fought between them in the Dryopid land, near the baths of Hercules (the place of the baths is identified by certain researchers near the current village Hanopoulo). Arbitrator to the fight of gods was Kragaleas, a local hero, which according to the myth, judged that Amvrakia should be given to Hercules. Apollo however was angry about it and transformed Kragaleas into a rock. At 625 B.C. Corinthian settlers leaded by Gorgos, illegitimate son of Kipselos, tyrant of Corinthus, founded Amvrakia, at the place that today the town of Arta is located. The town was built at the left bank of river Arachthos, at the foot of Peranthi hill and at a relatively small distance from the Amvrakikos gulf.
According to ancient literarure testimonies Amvrakia took the name from Amvrakas, son of Thesprotos, while an other version connects the name with Amvrakia, daughter of Melaneas. At the 6th century B.C. the town was an important centre of Corinthian trade in north-western Greece and an important turning-point for its travels to South Italy. From this place the Corinthians promoted their merchandises in the continental hinterland, which supplied them with crude raw material. The growth of city is confirmed by the ancient writers, but also by the excavations in the town. Amvrakia took part in Persian wars and participated with important force (with seven boats in the naval battle of Salamina and with 500 soldiers in the battle of Platees). During the Peloponnesian war Amvrakia remained faithful to metropolis Corinthus, which it also helped during Corinthus war operations against Corfu.
At 295 B.C. Pyrros, king of Mollossoi, transported in Amvrakia the capital of his state, which then became the base of operations of his expeditions against Romans. Pyrros gave international glamour to the town, as well as in entire Epirus and adorned Amvrakia with important buildings. The ancient town was built according to the Ippodamio system and had appreciable buildings and imposing walls, from which an important part is saved up to our days. A big Dorian temple of Pythios Apollo was found in the centre of the current town (King Pyrros street) and near this place, the small theatre was recently revealed.
At 189 B.C. Amvrakia after vigorous resistance, was forced to accept the Roman guard. It was for this reason that the town avoided destruction, when few years later, at 167 B.C. Roman general Emilius Pavlos destroyed 70 continental cities and led to the captivity of 150.000 people of Epirus. After the foundation and the settlement of Nikopolis at 29 A.D., Amvrakia stopped playing an important role in the region, however it does not appear to be abandoned completely, as the last discoveries of excavations show. For the wider region of Amvrakia (meaning the region within the limits of current prefecture) no historical information exists. In the region however ancient places have been located occasionally, in which however, except small exceptions, no important archaeological research has been taken place. Antiquities have been located in Kompoti, Pitiana, Kipseli, Grekiko, Vourgareli, Peta, Dimario etc. Amongst them, the best known place is Kastri in Ammotopos, which is identified as the ancient city of Mollossoi, Orraon, known from signs of the 4th - 2nd century B.C.