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The National Library of Greece, Athens. More Athens Here
Some info:
The National Library of Greece was founded by I. Kapodistrias by a decree published on May 15, 1832. It was originally named the "Public Library," with George Gennadio serving as its first supervisor.

The original idea for establishing a National Library of Greece came from the philhellene J. Mayer, in an August 1824 article of the Greek Chronicle in Missolonghi, where Mayer had been struggling alongside Lord Byron for Greece's independence. Mayer's idea was carried out in 1829 by the new Greek government of John Kapodistrias, who grouped together the National Library with other intellectual institutions such as schools,
national museums, and printing houses. These were all placed in the Aegina's Orphanage, under the supervision of Andreas Moustokzidis, who thus became president of the committee of the Orphanage, director of the National Museum, and director of the National School.
Source: here