The beginnings of Metropolitan library are reaching into the 11th century, to the time when Zagreb is becomnig a bishop town (1093/1094). In the time of the first zagrebian bishop Duh, the first liturgy books were also obtained.
Some manuscripts from that period of time such as Evangeliarium, Sacramentarium sanctae Margaretae, Agenda pontificalis are kept in Metropolitan library today.

Biblia soliemnis Gothic script, 14th century, France CSA, Metropolitana library		Evangeliarium Caroline, 11th century CSA, Metropolitana library

This little group of liturgy codexes is a foundation of today's Library. The oldest inventory of the Zagrebian cathedral's treasury from 1349. testifies about the Metropolitan as a library , there are 111 registered manuscripts in an index of books, and 2 in an indeks of other liturgy subjects inside the trasury. Acording to the inventory, the grounds of the library were juridical, biblical, liturgical, filosophical and theological books. From codexes it's worth to mention the Biblia sollemnis, Liber sententiarum, Passionale and Benedictionale. During the time, Ivan Alben (1421 – 1433) perform function as a bishop a new inventory was made , the last one that brings such an indeks of books. Therefore it's very hard to keep track of the condition in Library during over the next 250 years.

The Metropolitan library reaches the true renesance in the time of bishop A. I. Mikulić (1688 – 1694), who builded the Library in 1692. and had all the books from the cathedral transfered in it. He established a foundation for it's work and bought of a very valuable book collection of known slovenian polyhistor J.W. Valvasor (1641 – 1693).
S. Želiščević, an inheritor of A. J. Mikulić, published the first Constitutions of the library in 1695., but great credits are due to two more bishops for the advancement of the Metropolitan library. M. Vrhovac (1787 – 1827) provided literature for Metropolitan library from different european states, he listed books, enlarged the foundation for the functioning of the library, and especially, took care of books being printed in Zagreb.
In 1846. bishop J. Haulik opened the Library to the zagrebian cultural public, and he, himself, left a large number of books to the Library. In the year 1914. a contract between the Archbishopric of Zagreb, Metropolitan Chapter House (Kaptol) and Nacional and University Library was concluded about temporarly storage of Metropolitan library in new building of Nacional and University Library. The owner of the Metropolitan library continues to be the Archbisopric of Zagreb. The contract about storaging with, today's owner of the building, CSA, was concluded in 1996.
The Metropolitan library keeps books from, almost, every area of science and culture. It possesses about 150 older manuscripts (11th -16th century), amongst which are many richly illuminted and are world's rarities. Fifty manuscripts from period of 17th till 19th century are included in rarities of the Metropolitan library (label MR). This Library also keeps the biggest collection of incunabulums in Croatia (252). It possesses around 300 «younger manuscripts» (18th – 19th century), and especially valuable is collection with nearly 1500 titles from the 16th century which, today, are counted among rarities. From small but valuable atlas and geographical maps collection, atlases from Ortelius and Janson stand out.

The Metropolitan library today, has around 60.000 volumes of books. Special value represents, already mentioned, the Valvasor library, whose books are from, almost, all scientific areas, mostly decorated with copperplates of a familiar copperplate engraver M. Merian. During his lifetime J.W. Valvasor gathered a valuable graphic collection with approximately 7.300 graphics and drawings created in period from 15th till 17th century.
He bought a smaller part as a collection from slovenian painter G. Wubitsch, and a bigger part he collected on his journeys through Europe. At the end of his lifetime, he sold the collection, through P. R. Vitezović, to the Zagrebian bishop A. J. Mikulić.
All the significant graphic artists from 15th till 17th century like A. Dürer, L. Cranach, M. Schöngauer, G. Penz, families Kilian, Sadeler and Perelle are represented in the collection. The collection is thematically diversified – except the religious themes, there are plenty of graphics and drawings with themes from everyday life. Apart from artistic value, this collection has a huge culturaly –historical significance as it is the largest and the most significant collection of old graphics and drawings in Croatia

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