The £26m site near Swindon, Wiltshire, has 153 miles (246km) of shelving.
The library, which is entitled to a copy of every book published in the UK, had been running out of space to store works for decades.
With 1,000 new books arriving each day, the head librarian said the situation had become “desperate”.
The new warehouse has enough space to support the Bodleian for the next 20 years.
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