This is a historic municipality, inhabited since prehistoric times. Excavations have uncovered rectangular houses from the prehistoric era, as well as copper processing facilities. Rafina was one of the 100 municipalities of Athens designated by Cleisthenes, under the name “Araphen.” It was named after its first governor, Araphen, who was one of the 100 heroes of Attica. Excavations in the area have also revealed elements from the Roman period (buildings, a Roman bath, statues). Ancient Rafina was located above the port. In the location Askitario (Marikes beach), fortified settlements from the early Bronze Age were found.

The modern history of Rafina begins in 1923, when the residents of Triglia in Bithynia, Asia Minor—the birthplace of the Hieromartyr Metropolitan of Smyrna, Saint Chrysostomos—arrived in Greece on ships provided by the Triglian shipowner Philippos Kavounidis.

The Greek government proceeded to expropriate the Skouze estate, which was granted to the refugees from Triglia. Gaining a new homeland, the Triglian refugees, known for their energy and spirit, built and developed a new Rafina. Some dwellings were also allocated to refugees from Vourla, Karamanlides, and others.

In 1928, the community of Rafina was established, with its only significant settlement being Rafina Junction, which, even before the arrival of the refugees, was inhabited by workers from a lignite mine (mostly from Evia). In the following decade, Rafina became known for its strong growth in tourism and the utilization of its port. During the dark years of the German Occupation, the headlands near the port of Rafina were filled with pillboxes, while the hill on the south side of the stream was turned by Rafina locals—forced into labor by the Germans—into a fortress, as indicated by its current name. Nevertheless, Rafina served as an escape route for military and political figures.

The post-war period saw Rafina in a successful effort of economic and social reconstruction, supported mainly by the modernization of the port, a series of essential, functional projects, and the construction of buildings. The first vacation homes were quickly built, providing work for many locals, and the first small hotels were established. The Rafina Junction road was paved, wells were drilled, taps were placed at many corners of the settlement, and the Rafina Electric Company was founded by the Chrysogelos brothers, along with an ice plant.

In 1994, Rafina was officially recognized as a municipality. Today, Rafina is a beautiful, coastal, modern town that retains its character and respects its identity. It cherishes its residents and attracts many vacationers and visitors. Currently, Rafina is effectively a suburb of Athens, thanks to the Attiki Odos highway, which has improved access from the city center.