Under 'Book Ahead', public libraries can choose free books from a new list compiled by the School Library Association.
Up to half a million free volumes will be given away to local nurseries in book boxes made up by the libraries.
The DCSF said that the boxes would include new picture books, classics, stories to read aloud and tips for parents.
Mr Balls said, 'We must get young children into reading as early as possible - particularly boys and their dads.
'Early exposure to books affects learning. A child from a deprived home has heard just 13 million words by the age of four, compared with 45 million in a more affluent home. What starts as a problem with vocabulary rapidly turns into a problem with reading, writing and comprehension, leading to poor exam results.'
The Book Ahead scheme was announced as an international study of reading showed that England had fallen from third place to 19th in a literacy league table based on 215,000 ten-year-olds in 45 countries.
The scheme will kick off next year's National Year of Reading.
FURTHER INFORMATION
PIRLS: Progress in International Reading Literacy Study is at www.nfer.ac.uk.