We've just come back from a cruise around the Med including Pireus. It's so simple to go by Metro to the centre of Athens. It's out of the terminal and turn left. Keep the ferries on your left and keep going until you get to an overbridge (about 20 minutes walk) this bridge takes you over the road to the station. Trains are very frequent, fare is 70 cents single and Monastiraki station is 7 stops (about 10-15 minutes.
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