In a kiss-and-tell memoir, written and published in the utmost secrecy, Valerie Trierweiler charts the highs and lows of her time with Hollande, whose popularity is already at historic lows and who could suffer further embarrassment from the new revelations.
In extracts published today by glossy magazine Paris-Match, Trierweiler describes the bust-up in the presidential bedroom when news broke of Hollande's affair with actress Julie Gayet.
"I crack up. I don't want to hear that, I rush into the bathroom. I grab the little plastic bag with the sleeping pills," she recounts in an episode run in the magazine.
The 320-page book "is a cry of love as well as a slow descent into hell, a plunge into the intimacy of a couple. Two people and nothing more: Valerie and Francois," the weekly writes.
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Hollande's office said it was "not aware" of the book's publication. "So by definition we have not read this book," a source close to the Socialist leader told AFP.
Hollande subsequently left Royal, the mother of his four children, for Trierweiler who became the de facto first lady of France after he was elected in 2012, despite the fact the pair were not married.
In quotes carried by Paris-Match, Trierweiler says that at the beginning, "it was electric between us when we were together."
But Hollande changed, "de-humanised" as he got closer to the reins of power, Trierweiler was quoted as saying by the weekly.
According to Paris-Match, Stephane Le Foll, a close advisor and now government spokesman, told her: "If you want an evening with Francois, you have to go through me."
Then once elected, Hollande pulled further and further away.
She recalls an episode before a state dinner, when he asks her whether it takes her a long time to be "beautiful", to which she responds in the affirmative.