The show documents each of the Presidents in the union, starting with George Washington, following a chronological order up until George W. Bush. Each President's segment begins with the narrator giving a brief dossier about each one, from their political affiliation, family, and notable traits. The show then highlights the history behind each presidency, linking each one to the following.

Edward Herrmannas Narrator
Annette Gordon-Reedas Annette Gordon-Reed
Daniel Walker Howeas Daniel Walker Howe
Harry Watsonas Harry Watson
John Seigenthaleras John Seigenthaler
Rhys Thomas
Earl Rose