- Nicole Kidman was originally cast as Mrs. Smith.
- Johnny Depp was originally cast as John Smith, but turned it down after being overworked with other movies he was shooting.
- Catherine Zeta-Jones was also considered for Mrs. Smith, while Johnny Depp and Will Smith were considered for Mr. Smith when it was not sure if Brad Pitt would sign on.
- Cate Blanchett was also considered for the role of Mrs. Smith
- Brad Pitt reportedly left the project after Nicole Kidman dropped out and her replacement had not yet been found. Once Angelina Jolie signed on, he returned to the project.
- In order to get a wider PG-13 audience, a very steamy sex scene between Brad Pitt and Angelina Jolie was cut.
- The script reportedly went through over fifty drafts. Although original writer Simon Kinberg was the final writer during production, various uncredited writers worked on drafts throughout the film's development, including Jez Butterworth, 'John Butterworth', Carrie Fisher, Akiva Goldsman, Ted Griffin, Kieran Mulroney, Michele Mulroney, and Terence Winter.
- Brad Pitt left in the middle of shooting for three months to shoot Ocean's Twelve (2004).
- Near the end of the story, when Benjamin is being interrogated by the Smiths, he is wearing a Fight Club shirt. Brad Pitt starred in Fight Club (1999).
- Was shipped to theaters under the code name "Jones".
- The original ending featured villains played by Jacqueline Bisset and Terence Stamp. After this was dropped, a second ending was filmed with Angela Bassett and Keith David as the villains. This too was dropped when it was decided that the film did not need a final confrontation with the villains at all.
- Many of the scenes from the trailer were not in the movie, including Brad Pitt riding a bike while shooting and Keith David ordering someone to "bring in everyone," after finding out "it's the Smiths".
- Angela Bassett was cast as Mr. Smith's boss but her scenes were subsequently cut from the film. Her voice is still heard in the film, giving him instructions of his next assignment.
- Gwen Stefani was considered for the role of Jane Smith after Nicole Kidman dropped out.
- The 35mm prints of this film come from a digitally grain reduced digital intermediate. They are full of digital grain reduction artifacts.
- I-Temp is located in Suite 5003 at 570 Lexington Avenue. The building is real and it has 50 floors.
- When Jane and John are discussing past assassinations, John refers to Jean-Luc Gespar, which was the real name for the character LaMarc in Ocean's Twelve (2004).
- Aishwarya Rai was the first choice for "Jane" but she turned it down due to filming dates.
- Body count: 43
- In the scene where John Smith is in his office a black suit with a white shirt and red tie can be seen hanging in the background. This is the same outfit worn by "Agent 47" in the popular Hitman game series.
- Script-writer Simon Kinberg names The Long Kiss Goodnight (1996), Prizzi's Honor (1985), The War of the Roses (1989), True Lies (1994) and the The Thin Man (1934)-series as inspirations for his script for this movie.
- The film's original script was actually writer Simon Kinberg's thesis for his Masters in Fine Arts.
- Jolie's Jane and Pitt's John ranked #3 on Moviefone's 'The Top 25 Sexiest Movie Couples'. [May 2008]
- In the department store, after identities have been uncovered and Mr and Mrs are facing the enemy together, brief respite is provided as they take the elevator in which "The Girl From Ipanema" is playing. This is redolent of a similar elevator-based pause in festivities which occurs in The Blues Brothers (1980)), which is a trademark of director John Landis) and which may be a nod to him from this movie's director, Doug Liman.
- The shot of the helicopter flying over Bogotá at the start of the flashback sequence was originally used in Clear and Present Danger (1994). For its appearance in Mr & Mrs Smith, CGI was used to enhance it with burning buildings and someone sitting in the rear passenger seat of the chopper.
- Eva Green was considered to play Jane.
>>> WARNING: Here Be Spoilers <<<
Trivia items below here contain information that may give away important plot points. You may not want to read any further if you've not already seen this title.
- SPOILER: After the Smiths discover each other's identities, Jane speeds away in the car and John is running after her. He ends up tripping and crashing through a fence, and his gun goes off. The trip was a mistake, and Brad Pitt's reaction, as well as his following ad-lib, "Oh dear God," are genuine.
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