Valerie Trierweiler claimed in the book that the Socialist leader jokingly referred to the destitute as "toothless" in private.
She was the president's partner for nine years until he brusquely ended their relationship following revelations he had an affair with an actress.
In the memoir, entitled "Thank You for the Moment", Trierweiler writes that Hollande "portrayed himself as the man who doesn't like the rich. In reality, the president doesn't like the poor."
"I don't want people to be able to say or write that I don't care about suffering in society, because that's a lie that hurts me," Hollande said yesterday.
"This attack on the poor, the most disadvantaged, I took it as an attack on my entire life."
The president said in every political post he had held "I have thought only of helping and representing those who are suffering".
"I have never been on the side of the powerful, even if I am not their enemy, but I know where I come from," he said.
Its publisher said 145,000 copies were sold in the first four days and it has ordered a further print run of 270,000 copies.
Hollande angrily rebuffed the former first lady's accusations on Friday at a press conference after a NATO summit in Britain, and did so once again in the interview.
"Yes, I met people suffering the worst kinds of hardships, worn down by life. They had trouble caring for their teeth. That's the sign of the worst kind of misery. I rubbed shoulders with these people, helped them, supported them," he said.
Fifty-six per cent believe she was "wrong" to write the book, according to a poll by Harris Interactive for VSD magazine, while 67 per cent were opposed to the memoir in a CSA survey.
The interview came as Hollande was dealt yet another blow when his finance minister said France was again delaying its target to hit EU deficit rules and revising down its growth forecast.
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