The artefacts at the University of Oxford's Bodleian Library are currently accessible only to a few scholars.
The gift, from Oxford publisher Julian Blackwell, will go towards the creation of an exhibition hall at one of the library's sites.
Other treasures include an embroidered handwritten book by Queen Elizabeth I.
The Bodleian Library has a copy of almost every book printed and an extra 5,000 books are added to its catalogue each week.
It is the main research library for the University of Oxford and occupies several sites across the city.
The new centre will be named the Blackwell Hall in recognition of the donation and will form part of a £70m redevelopment of the New Bodleian Library.
"The Bodleian is unique"
Four original copies of the Magna Carta, written in the 13th Century, and one of only eight Gutenberg Bibles are among the artefacts held by the library.
The earliest complete book written in English, Gregory the Great's Pastoral Care, translated by King Alfred in about 890 AD is another of the treasures.
There are also many original handwritten texts of popular classics such as Frankenstein, as well as more than 10,000 medieval manuscripts.
Controversial plan
Richard Ovenden, keeper of special collections at the library, said: "Julian Blackwell's magnificent donation to the Bodleian reflects the long established connections between these two institutions.
"Not only are they neighbours on Oxford's Broad Street, but for 130 years they have jointly engaged in projects which have both celebrated and preserved our global written heritage."
Mr Blackwell added: "The Bodleian is unique.
"It not only has the largest and most important university collections in the world, but it is leading the development of cutting-edge information services which are so vital to academic research."
Margaret Hodge, minister for culture, media and sport is due to attend an event on Saturday in honour of the library's founder, Sir Thomas Bodley, when the donation will be formally announced.
In November controversial plans to build a £29m book depository to help ease storage problems at the library were turned down by the city council because critics said the building would ruin the city's skyline.
The university said it would appeal against the decision.
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