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To reach central and northern Evia from Athens, most people drive via the bridge at Halkida (Chalcis) - but be prepared for slow and winding roads beyond Psachna. Alternatively, for the northern tip, you can follow the E75 motorway further up to Arkitsa and take the regular ferry to Loutra Edipsou, an easy half-hour crossing.
To reach southern Evia from Athens, it's simplest to take the ferry from Rafina to Marmari or Karystos; there's also a less regular ferry from Ramnous (near Schinias beach) to Nea Stira.
Evia also has ferry connections from the town of Kymi (on the east) to the island of Skyros, and from Agiokambos (in the north) to Glifa where you can rejoin the E75 motorway for the northern mainland.
See Around Evia for more details.