The as-yet-untitled album is the follow up to 2005's I Am Me.
Fall Out Boy's Pete Wentz denied any involvement in putting the unusual pair together, even though both of them are his personal friends.
He said: "I doubt I had anything to do with it, 'cause they were friends since she was performing in Chicago. But I definitely only have good things to say about Ash--I think the collaboration could be great."
Simpson is also known to be working with Keane's Tim Rice-Oxley, Chad Hugo from the Neptunes, and John Legend, reports Entertainment Weekly.
For more music news, go NME.com.
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