Hollande, speaking after an emergency EU leaders summit in Brussels, said the €100 million would be spent over two years.
The summit in Brussels resulted in the EU agreeing to throw €1 billion at aid agencies working with refugees, and to help those countries hosting millions who have fled Syria and Iraq.
"Member states must also make their own supplementary contributions," said Hollande
"I am thinking particularly of my country...which must release more means that initially expected."
"This is money that we cannot spend elsewhere because if refugees come to our country, looking for asylum, we will welcome them and we know that there are financial implications."
The money will go towards those living in refugee camps "so men, women and children can live in dignity".