The Rare Book and Special Collections Reading Room of the Library of Congress holds a modest number of rare books of Serbian interest or origin, but several of the items are plum pieces for the collection such as two srbulje (sing. srbulja), the first of which is Minej prazdničny: sʹbornik [Holiday Menologion: Collection]. Published in 1538 in Venice by Božidar Vuković, a printer from the Podgorica area, Minej prazdničny is the first edition in any Slavic language of the Menologion, a monthly Orthodox Eastern ecclesiastical calendar with biographies of saints and prayers for each day. With numerous woodcuts, head-pieces, and decorative initials, the 1538 Menologion is the most illustrated early Cyrillic book. A blog post reveals more details and images of the Library's copy of the Menologion. The second srbulja in the Library of Congress rare book collection is the 1638 Psaltir, the final srbulja published in Venice. Like the Menologion above, the language of the text is the Serbian recension of Church Slavic, the written language of the Serbs from the 12th century to the 1830s. The image to the right is from this volume.

Other Orthodox works of note in the collection include Gospoda nashego spasitelę Slovo ō věchnom blazhenstvū [Our Lord and Saviour's word on eternal blessedness] from 1821 and written by Lazar Miletic (1776-after 1845) about The Beatitudes. This item once belonged to Prince Aleksandr Nikolaevich Golitsyn (1774-1844) and was acquired in 1906 as part of the Yudin Collection. Among the earliest Serbian items ever added to the Library of Congress are three editions of the Bible translated into Serbian - from 1857, 1867, and 1869, all from different printing houses, but using the same translation of Platon Atanacković (1788–1867). The Bibles have old 19th-century LC bookplates or stamps showing that they were added to the Library in the late 1870s. Two different facsimiles (1897 and 1998) of the Miroslavovo Evanđelje [Miroslav's Gospel] also reside in the Rare book collection. The edition from 1897 was a gift from King Milan Obrenović of Serbia (1854-1901) at the end of the 19th century. In addition, as part of the former World Digital Library, the Library of Congress shares on the its website a digital copy of the original manuscript housed in the National Library of Serbia.

A landmark work of interest to all of the South Slavic nations is the original 1601 printing of Il regno degli Slavi hoggi corrottamente detti schiauoni [Realm of the Slavs] by Mauro Orbini (1550-1611), a Benedictine monk from Dubrovnik (Ragusa). Although Orbini incorporated unsubstantiated legends and chronicles, his history of the Slavs, with a special focus on the South Slavs, also relied on many other sources including works by Orthodox and Protestant writers which were banned by the Vatican, resulting in his work being banned as well in 1603. Also in the Library of Congress Rare Book collection is the 1722 Russian translation of Orbini's history Knīga Istorīograḟīi︠a︡ pochatīi︠a︡ imene, slavy, i razshīrenīi︠a︡ naroda slavi︠a︡nskogo [Book of historiography on the origins of the name, glory and expansion of the Slavic people], translated by Sava Vladislavić (1669-1738), a diplomat from Herzegovina and Dubrovnik who served on behalf of the Russian tsar Peter the Great. Il regno degli Slavi and its Russian translation were of enormous significance for the historiography of the South Slavs and the Pan-Slavic philosophy.

From the 18th century and published in Leipzig is the first edition from 1788 of Ezopove i prochikh raznikh basnotvort︠s︡ev... basne [Fables of Aesop and other fabulists], a Serbian translation of Aesop's fables by Dositej Obradović (1739-1811) who appended part of his autobiography to the end of the work. From another noted Serbian cultural figure is the 1828 work Imeslov, ili, Ri︠e︡čnik ličny imena razny naroda slavenski [Imenoslov or dictionary of personal names of various Slavic peoples] compiled by the Serbian poet, soldier and painter from Baja Jovan Pačić (1771-1849), with the assistance of the Slovak proponent of Pan-Slavism Ján Kollár (1793-1852). With articles and images from across the Balkan peninsula is Srpske ilustrovane novine za zabavu, pouku, umetnosti i književost [Serbian illustrated newspaper for entertainment, education, art, and literature], a folio-sized weekly newspaper published in Serbia from 1881 through 1882.

Also from the 19th century are works of cultural and historical significance to Serbia's neighbor Bulgaria. In 1830 after the Serbs won autonomy from the Ottomans, Miloš Obrenović, Prince of Serbia (1780-1860), set up a Cyrillic printing press and allowed several Bulgarian works to be published in his territory, for during these early years of the Bulgarian National Revival the Bulgarians were not allowed to publish in their own land. Several of these Bulgarian items published in Kragujevac and Beograd are held in the Early Bulgarian Imprint Collection, including the first Bulgarian geography textbook ever published Kratkoe politīcheskoe zemleopisanīe za obūchenīe na bolgarskoto mladenchestvo [Brief political geography for the instruction of Bulgarian youth] from 1835.

Twentieth-century rarities of Serbian interest in the Library of Congress rare book collection are more scattershot, but include among other titles a first edition with dust jacket of Rebecca West's 1941 classic Black lamb and grey falcon based on her travels throughout interwar Yugoslavia; several of Charles Simic's translations into English of Serbian poetry held in the Poets Laureate Collection; and three books on Serbia that were once owned by Woodrow Wilson. All materials held by the Rare Book and Special Collections Reading Room must be used onsite, unless there happens to be a digitized version on the Library of Congress website.