The Methana peninsula has been inhabited since about 10,000 BC. The first settlements were founded about 6,000 BC. Excavations have brought to light a village and sanctuary from Mycenaean times near the town of Methana at the chapel of Sts. Constantine & Helen. Items dating from about 1500–1200 BC are preserved in the museums of Poros island and in Piraeus city. There were ancient sanctuaries in Geometric times, about 800–700 BC, such as the Geometric temple near Kounoupitsa village. There are also two ancient acropoleis (Paliocastro acropolis and Oga acropolis) and many ancient farm sites. The ancient writers Ovid, Strabo and Pausanias described the historic eruption of the volcano dome near the village of Kameni Chora in the northwestern part of the Methana peninsula. Pausanias also described hot springs after the eruption. Later there were many new buildings and sanctuaries founded near the village Vathy, at the Paliocastro hill and around it. Methana was also the site of a Phoenician base called Arsinoe.
The earliest known settlement (near the village of Vathy) dates from 1500–1300 BC. The first survey was conducted by Michael Deffner, who discovered a large throne, among other artefacts. Many ancient sites were identified through the archaeological survey conducted in the 1980s by the University of Liverpool in association with the British School at Athens. The Acropolis Palaiokastro is located near the village of Vathy. The fortress is in Kypseli at the coast Akropolis Oga at the principal pace of Nisaki (Νησάκι, meaning little island). A Mycenaean settlement was excavated by Helene Konstolakis-Jiannopoulou in 1990 along with the chapel of Agios Konstantinos and Elenis. Selected artifacts can be visited in the museums of Poros island and in Piraeus. This site dates between 1500 and 1300 BC. In his History of the Peloponnesian War, Thucydides tells of an Athenian expeditionary force under Nicias that after defeating Corinth (in 425 BC) built a wall across the isthmus to cut the Methana peninsula off from the mainland.
In the Hellenistic period, the peninsula became one of the Ptolemaic bases in the Aegean when it was renamed Arsinoe. Traditionally, the population of Methana were Arvanites.
The peninsula is entirely of volcanic origin and contains over 30 volcanic eruption centers. The last volcanic eruption occurred near present-day Kameni Chora in 230 BC and a submarine volcano erupted in 1700. Famous writers such as Ovid, Strabo and Pausanias reported the last volcanic eruption in Methana. The peninsula is the northwesternmost of the arc of the Aegean islands of which the active volcanic areas are Methana, Milos, Santorini and Nisyros. In the future, Methana (and the area of the Saronic gulf) may expect other volcanic eruptions.