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You would not do a lot of hiking. It is not that close to Athens.
Have you been to Athens and the nearby sites - Corinth, Mycenae, Delphi,..?
If you have not, do that. You will do plkenty of hiking walking around the sites. The Loussios Gorge is very nice, especially around Dimitsana, but not to take you away from Athens. Save it for a road trip around the Peloponessus.