Old King Cole, published in 1985 by the Gleniffer Press in Paisley, measures only 0.9mm in height.
It held the world record for the smallest printed book, for 20 years.
It is one of about 85 miniature books from the library’s collections which will be displayed to the public for free until 17 November.
Exhibition curator James Mitchell said: “Many are works of art or miracles of technology and are highly collectable.”
A miniature book is generally defined as one that is less than 7.5cm (3in) in height and width.
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James Mitchell, who has been instrumental in building the NLS’s collection of miniature books, and who curated the new display, said: “Many are works of art or miracles of technology and are highly collectable. Old King Cole is produced using offset lithography, which is a version of the traditional Gutenberg method. They appeal to children because they are more of a scale for them, and for adults it’s about the artistry, design and execution.”