Anywhere on the main south road of the island is within fifteen minutes of the main town and in the town you can catch a ferry to Pireaus (Athens' port and then a 30 minute metro/bus journey) or catch a plane which run daily but would be more expensive..
Sorry the post above is wrong - There are no ferries to Piraeus from Skiathos. The Olympic flight works out around 10 euro more expensive, and there is just one a day.
Ferries go to Aghios Konstantinos with three hour bus transfer or Volos with 5 hour bus transfer
No ferries from Piraeus only Constantinos and Volos and then a buss to Athens
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