It marks only the fifth time in the last 50 years that a day of mourning has been declared in France.
"Unity is our best weapon," Hollande said in a televised address, adding that flags would fly at half-mast across the country for three days.
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The president praised the "courageous chroniclers" of Charlie Hebdo.
Eight of its journalists, including four of the country's best-known cartoonists, were killed in the attack at its office in central Paris earlier in the day.
"They touched -- by their influence, by their insolence, by their independence -- generation after generation of French," Hollande said.
"This message of freedom, we will continue to defend it in their name.
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