The steep castle hillside played a strategic role also in the early Iron Age. The people of Kalenderberg culture lived in the Devín hillfort mostly in dugouts, but also in above-ground shelters with woven or wooden walls.

At the end of the Iron Age, the Celts came to the Devín area and settled there for approximately hundred years. In addition to their dwellings, archaeologists unearthed also other structures related to crafts, such as pits, ovens and workshops. Of particular importance is the uncovering of specialized smith and jeweller‘s workshops with a collection of tiny iron and bronze items. Contacts of Devín Celts with the Roman Empire in particular can be evidenced by finds of terra sigillata, iron items, but especially coins. Celtic settlement was destroyed in the 20s–30s AD by German tribes. Strategic location of the Devín hillfort enabled and contributed to the development of cultural contacts and trade. At the end of the 1st century BC, the Romans moved their border to the north. Within this Roman occupation, also Devín was included into the sophisticated fortification system called Limes Romanus as one of the strategic outposts of the Roman camp in Carnuntum. At the beginning of the 1st century AD, direct presence of Romans in Devín is highly probable.

The oldest Roman settlement can be documented by foundations of a wooden tower and by a number of small finds. The locality of Devín Castle is unique also in terms of Roman stone structures – overall, remains of as many as four Roman stone structures were uncovered here. The biggest one can be found in the courtyard of the Middle Castle and was dated to the 3rd century with a younger reconstruction in the 4th century. Noteworthy is the stone building dated to the end of the Roman era that used to be located on the grounds of the Lower Castle and may have been used as an early Christian religious structure. The migration period did not leave many traces in Devín, the most interesting of them is definitely the carbonized loaf of sourdough bread from the 5th century.

More intensive settlement of Devín area is recorded as late as the Great Moravian era. Devín hillfort became an administrative and power centre of this area with a massive fortification system made of wood and earth. This system included also small defensive forts called Na pieskoch and Nad lomom on the hillside of Devínska Kobyla. Devín’s strategical and military importance is testified by a military event in 864 that influenced also the politcal history of the Great Moravian state. In this year, Frankish ruler Louis the German besieged the Great Moravian prince Rastislav in a site called Dowina. We assume that Dowina can be identified with Devín near Bratislava.
The most important find from this period is represented by foundations of a church with longitudinal nave with east–west orientation. It was divided with three partitions into 4 parts and ended with 3 apses in the east. Its interior was decorated with paintings featuring plant and figurative motifs as evidenced from uncovered fragments of polychrome plaster. South of the church‘s foundations, the research unearthed six Great Moravian tombs with rich funeral furnishings. Burial on a central burial place near a religious building and the character of finds in the tombs indicate higher social status of buried individuals. Other inhabitants were buried on three burial sites located within the borders of present-day district of Devín. The biggest one of them – today’s location Za kostolom next to the Church of St. Cross – was researched and 123 tombs were uncovered.

The settlement in Devín was more or less continuous even after the fall of the Great Moravia as demonstrated by a vast early medieval cemetry and a street-type hamlet uncovered on the grouds of Devín Castle. In the 13th –14th centuries, Devín was a royal castle and served as a border fortress of the Hungarian kingdom. In the 13th century the castle saw frequent battles and was destroyed on several occasions. In the Upper Castle, the research helped to uncover foundations of a tower from this period, in the middle of which there was an entrance to the caves in the castle rock. The castle and village flourished only at the beginning of the 15th century. In 1414 Nicholas II Garai (†1433) bought the right to the castle from the Vienna burgher Ladislav Hering and the king pawned the castle to him and his male descendants. In 1419–1460 Garais carried out extensive structural changes and built fortifications, a residential palace in the courtyard of the Middle Castle and rebuilt the Upper Castle. Subsequently, they also fortified the lower part of the castle, built a polygonal tower, western gate and had 55 metres deep castle well dug up. Next owners of the castle were the counts of Svätý Jur and Pezinok (1460–1521) who focused especially on further strengthening of fortifications. They built eastern gate and also northern gate with a guardhouse facing the town of Devín.

In 1527 the emperor Ferdinand I. Habsburg lent the castle and its domains to the Hungarian palatine Stephen Báthory. Members of this family built a new palace wing in the Middle Castle next to the northeastern fortification wall and had other parts of the fortifications erected. On the top of a steep rock over the confluence of the Danube and Moravia they built a small polygonal bastion with crenellations. This turret gave rise later on to many legends and started to be called Virgin Turret or Nun. The last noble family owning the castle from 1635 were the Palffys. During their time, Devín did not undergo distinct architectural changes. In the Baroque period, the Castle was used only for economic purposes and administration of the Devín domain. At the beginning of the 19th century, Bratislava and its surroundings became the scene of Napoleonic wars which were disastrous for Devín Castle. In 1809 French soldiers mined it and blew it up. After this incident the Pálffys lost interest in the Castle and its ruins kept deteriorating. In 1932 the Czechoslovak Republic bought the castle from the Pálffys for symbolic 1000 Czechoslovak crowns. In 1961 Devín was proclaimed national heritage site.