The National Library is rightly considered one of the most important institutions which hold an important number of bibliophile valuables. We care to mention, that the conditions of preservation of these patrimonial valuables are very good, and the staff of bibliographers in the Department of old and rare book has a good attitude towards the bibliophile patrimony. This subject has been discussed in several previous articles, which, we believe, are useful for the researchers in the field. In this article we try to add some important details concerning other unique publications in the above mentioned collection of the National Library. Beside other old books there are two books by Dosoftei entitled Molitvenic de’nţăles (Molitvenik to understand), printed in Iasi, at the Metropolitan printing house, in 1681, and Parimiile (Advice), published in Iaşi at the Metropolitan printing house in 1683; an Octoechos, printed at the publishing house of Duca Sotiriovici in 1749; a edition entitled Strastnic (a book that contains the ritual of services celebration in the of Holy Week), published in Blaj, at the publishing house of Annunciation Monastery in 1773; an edition of Homilies by Macarie Eghipteanul, published in Bucharest, at the Metropolitan printing house in 1775, etc. The National Library of the Republic of Moldova is considered one of the leading institutions in the field which hold unique documents, because it has such bibliophile valuables. We would like to point out that many of them have not been found in other specialized collections or monastery libraries recently restored. These books are of major interest for our culture and spirituality. Their graphic appearance shows the level of culture of the Romanian society in different periods of its development, and the manuscript notes offer a broad range of topics to be considered by researchers, that is they can greatly contribute to the completion of our national history. in Odessa.