The Rare Books Collection holds the library's oldest and most valuable publications.

The books are all catalogued and individual items are available for viewing within the library upon application to a library staff member. They include

• old and rare books and pamphlets
• fine and limited editions
• Lutheran Church of Australia publications
• items related to South Australian history

The most beautiful item in the collection is Martin Luther's translation of the Bible in a 1551 edition with coloured illustrations. These coloured woodcuts have been digitally photographed for preservation and use for academic purposes.

Other valuable items are two original editions of the Book of Concord from 1580. This book contains the foundational confessions of the Lutheran Church in the original German.

The three earliest prints in the collection appeared in consecutive years:

• 1521 German translation of a much older book on the priestly office by Ambrose, 5th century bishop of Milan.
• 1522 Paraphrases of the Epistles of Paul by Erasmus of Rotterdam.
• 1523 Reprint of Luther's pamphlet explaining why women may leave cloisters.