The Cambridge University project will begin with a correspondence - some 1,400 letters - with his closest friend, the botanist Joseph Hooker.
It was to him that a devastated Darwin wrote in 1876: "I am sure you will pity us, when you hear that Amy was seized with convulsion which lasted for several hours, she then sunk into a stupor and I saw her expire at 7 o'clock this morning."
Cambridge University Library houses the world's largest and most significant collection of Darwin's personal papers. The archive - some 9,000 letters - includes correspondence with leading thinkers of the day.
There are also notes from the famous Beagle voyage, and the earliest manuscripts outlining his theories, which scandalised Victorians by suggesting animals and humans had a common ancestry.
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But no correspondence was more important to Darwin - or to scholars - than the Darwin-Hooker collection, according to Alison Pearn, Associate Director of the Darwin Correspondence Project.
"In perhaps his most famous letter of all, Darwin wrote to Hooker in 1844 of his growing conviction that species 'are not ... Immutable' - an admission he likened, half-jokingly, to 'confessing a murder'. It was also to Hooker that Darwin sent the manuscript of On the Origin of Species for comment," Pearn said.
Of their letters, 300 have not been published before.
In another letter to Hooker, Darwin poured out his grief at the death of his daughter-in-law aged 26. She was the wife of his son, Francis.
"I don't know of another letter [like it]. I don't think there are many people to whom [Darwin] would have written in this way. This is unique insight into his attachment to his daughter-in-law," Pearn said.