In addition to the books being given out tonight, a further 620,000 will be distributed in the UK over the course of the year to prisons, care homes, hospitals, sheltered housing, homeless shelters, libraries and other partner charities.
The initiative, which was launched last year to inspire a love of reading and to help improve literacy rates, is made possible by the pro bono contributions of the publishers, authors and production partners involved.
UK book printers CPI and Clays were responsible for printing more than 1m books for the event, after the World Book Night committee selected the 25 titles for this year's giveaway, which has gone international with sister events being run in Ireland, Germany and the USA.
Kate McFarlan, managing director at Clays and member of the steering committee for World Book Night, said: "The feedback we have received so far is that the event has been very successful.
"The steering committee meets in mid-May and by then we should be able to see if there has been any impact on the sales of the titles that were selected for WBN this year. Last year saw a significant increase in sales for WBN books."
CPI UK marketing communications manager Dino Bishop said: "We are very excited about World Book Night, and pleased to have been able to contribute to the event. We have been printing the books over the past three months at our Chatham and Croydon sites and it has been a very smooth process."
The date for this year has been chosen to mark the birth and death of Shakespeare, as well as the death of the Spanish novelist Cervantes.
Each of the 20,000 volunteers in the UK will be given 24 copies of their chosen book from the 25 WBN titles, which include Pride and Prejudice by Jane Austen, Notes from a Small Island by Bill Bryson, and Someone Like You by Roald Dahl.
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