The supplement will include features on football luminaries Jose Mourinho, Michael Carrick, Joe Cole and Michael Ballack, ahead of the final between Chelsea and Manchester United on May 19.
History of the competition and memorable FA cup goals will also feature in supplement.
Stuart Taylor, commercial director of Guardian News & Media, said: "This is a great collaboration between The Observer and E.ON. Both teams worked closely together to produce this exceptional souvenir supplement."
Simon Breakell, sports promotion manager at E.ON, said: "With exclusive content, interviews and expert analysis, this FA Cup souvenir supplement provides sport fans with the definitive guide to this year's FA Cup."
The Observer has had a fairly steady performance in sales this year, with the most recent ABC figures indicating a 3.07% increase in circulation to 455,707 copies during March. However, the paper's six-month average was down 3.9% year-on-year to 453,277 copies.