Bridesmaids actress Maya Rudolph, Green Day and Ferrell's former Saturday Night Live co-star Molly Shannon will also perform, as well as Lorne Michaels, Paul Rudd and John C. Reilly.
Ferrell will be the 14th recipient of the prize, to be handed out on October 23.
Will Ferrell: The Kennedy Centre Mark Twain Prize will air on local PBS stations on October 31.
The actor had previously said of the prize: "I am truly honoured to receive this distinction. I will now begin cultivating a Mark Twain-esque moustache in anticipation of the event."
Ferrell said earlier this year that he "doesn't get" why Anchorman 2 continues to be delayed.
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