The 35-year-old man was detained after a tip-off from library bosses about texts and pamphlets that had gone missing over a period of time.
It is believed they had vanished from stores at the National Library, and some are said to be of importance to the State.
While it is difficult to put an economic value on the works, a number are understood to be antiquities and of historical value.
Management at the Kildare St library became suspicious, and an audit suggested between 200 and 250 texts had vanished from the national collection.
Antiques and arts specialists from the Garda National Bureau of Criminal Investigation were called in to track down the publications. They carried out a dawn raid on a house in Clonsilla, north Dublin, at around 7am this morning. The man was arrested at the scene and the books and pamphlets were recovered within the house.
The man is being questioned at Lucan Garda Station under Section 4 of the Criminal Justice Act. He can be held for 24 hours.
It is understood the material is suspected to have been stolen over a period of time.
A spokeswoman for the National Library of Ireland refused to disclose which items in the publicly-owned national collection were missing. She said the matter was subject to a Garda investigation and there would be no further comment.
The National Library houses books, maps, manuscripts, music, newspapers, periodicals and photographs which document life in Ireland.
The Genealogical Office, the Office of the Chief Herald and the National Photographic Archive in Temple Bar are all part of the National Library.
The main building is next to Leinster House on Kildare St.