"December 1, 1903: Edwin Porter's The Great Train Robbery debuts. The plot: a wisecracking former cop fights train-jackers at 15 mph. Thrilling audiences with its pioneering realism and papier-mache trains, the final scene — in which the villain turns and fires his gun directly into the camera — was said to have so terrified the audience that they would often shriek in terror, screaming out 'Yippie ky yay, motherfucker!' as one."
When a character points a weapon at the camera so it looks like he is about to attack the audience with it. Sean Connery is not actually required; this just happens in a number of posters for his movies, such as the one illustrated here; as well as in several Bond film posters, most notably for Never Say Never Again.
The more aggressive Sister Trope of Pistol Pose, this trope is frequently used on movie posters, DVD/VHS cases, and book covers. The star of the work is pointing a gun directly at the audience. It's that simple.
Note that while this usually involves guns, other weapons and even fists can also be used. The "Superman Is About To Punch You!" variant, in particular, is quite common on comic book covers. And certain movies◊.
This trope is often used in movies themselves as well, although the MPAA prohibits its usage in green-band (all ages) trailers. If the character actually attacks the audience, it's The Fourth Wall Will Not Protect You.
See also Pistol Pose, Stab the Sky. Often overlaps with Floating Head Syndrome. Sword Pointing is a variation. Not to be confused with Bond Gun Barrel (which, nonetheless, often features this trope, sometimes literally).
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Anime & Manga
Not a cover or a poster, but pretty much par for the course for this series's promotional art: Noir - Kirika and Mireille◊ Are About To Shoot...Well, Everybody!
In the U.S. one-sheet for GoldenEye, Pierce Brosnan is definitely about to shoot you◊. He was actually so much about to shoot you in this advance poster that, according to the book James Bond: 50 Years of Movie Posters, the poster was rejected in the UK and several other territories!
Before it went Free To Play, Star Trek Online's box art featured a nameless white male human Starfleet captain pointing a phaser in roughly the direction of the guy standing next to the viewer. He got dubbed "Handsome Phaser Guy".
The Legend of Korra: Avatar Korra is about to punch...one or two centimeters to the left of your head. Her friend Asami, however, really is about to electrocute you right in the face.
Up to Eleven with Amor, "announcer" of the films of the German "Erotic note read: pornographic Animation" series. He does shoot at you, often wisecracking jokes like "This arrow is for he who never fapped". (FourthWall protects you, though.)
Anime & Manga
Alucard from Hellsing constantly makes it appear that he is aiming for the viewer's eyes.
The Killer does this a lot, most famously the scene where Chow Yun-Fat takes out his target at the restaurant during the first major shootout of the movie.
Not to mention the vision that Jenny has of Ah Jong firing directly at the camera, with a sea of blood behind him.
In Serenity, both Mal and River point their guns at the camera at different times, and at the end of the movie, River is glaring directly at the camera after slaughtering an entire army of Reavers, looking for all the world like she's about to take those bloodstained blades in her hands to the audience next.
When performing the theme song to The Three Caballeros, Panchito points one of his guns at the camera and it sings the lyric "and we'll stay so".
The second shootout (the one not dictated by Steve Buscemi) of Desperado features Antonio Banderas firing two full clips into the camera, and in the extras Robert Rodriguez points out that the force of the blanks and the closeness of the pistols knocked off the flash dampener.
A new poster had suddenly appeared all over London. It had no caption, and represented simply the monstrous figure of a Eurasian soldier, three or four meters high, striding forward with expressionless Mongolian face and enormous boots, a submachine gun pointed from the hip. From whatever angle you looked at the poster, the muzzle of the gun, magnified by the foreshortening, seemed to be pointed straight at you.
Live Action TV
Chris Elliott is about to shoot you in his domestic sitcom/cop drama mashup Action Family where he guns down his teenage daughter's scuzzy boyfriend - not that he's guilty of Chris's partner's death, he's just conveniently there for the wrap-up/happy ending.
In the Firefly episode "Heart of Gold," Mal levels his pistol dramatically at the camera, and then gets startled by Inara and lets out a very undramatic "Bwa!" of surprise.
In the Japanese commercials for the SFC port of Street Fighter II Turbo:
Guile is about to Sonic Boom you.
Chun-Li is about to Kikouken you.
Dante actually does kick the camera in the intro to Devil May Cry 3.
And an early trailer for Devil May Cry 4 consists of nothing but him unleashing a complete unholy beatdown on the camera.
One character's ending in Tekken Tag Tournament shows him delivering a beating to the camera. At the end, the camera arcs around to reveal he's beaten Heihachi and Kazuya Mishama senseless.
The cover for Mega Man Battle Network 5 Double Team DS does this with both Rockman.EXE and Protoman.EXE, not sure about Colonel.EXE
Mega Man and Bass opens up with the titular characters shooting King's Emblem. Then they emerge from the bottom of the screen, arm cannons smoking hot, and Bass is about to shoot you! Mega Man is waiting his turn.
Before all of these, IV for the Game Boy had its intro finish with Mega Man demonstrating his charged shot, straight towards the camera.
In the ending of Super Metroid, Samus will shoot the screen (and then, depending on how fast you competed the game, just give you a thumbs up, flip open her helmet, or show off what she looks like under her suit.
Fallout: New Vegas: The first thing your character actually sees in the game? Benny is about to shoot you. Justified, because that's the very next thing that happens.
The intro movie of Parasite Eve 2 ends with the main character Aya Brea doing a quick-draw and pointing her gun at the player/watcher. In the context of the actual game itself, she's pointing it at an army of Elite Mooks.
Occurs at the climax of Spec Ops: The Line. Take a close look at the angle Konrad's holding the gun in the event that you shoot him- he's not pointing it at Walker, he's pointing it at YOU.
Every boss cinematic in Sakura Samurai ends with them pointing their weapon directly at the camera.
Pokémon Platinum: Magmortar has its cannon pointed at the player in its basic sprite, and its animation acts like it fired a shot. Flint's Magmortar gets bonus points for having a Flame Seal on its Poke Ball laid over-top of its cannon, making it seem like it actually fired a shot.
In Batman: The Animated Series, Mr. Freeze fires his freeze gun directly at you. In the commentary, the directors are surprised they got away with it - they wouldn't have been able to with a regular gun, in case some kid decided to try it.
Real life example: occasionally in pro sports, an athlete or a ball will collide with a camera or cameraman. There is some pretty crazy footage from Major League Baseball of foul balls that have shattered the camera lens.
Many movies/games or other works featuring cars tend to do this with the cars themselves in a different fashion. For example, an Aston Martin One-77 is about to run you over◊!
Used for humorous effect on the cosplay/talk show/thing Demyx Time, where Vexen is using his mind-ray to make everyone forget about the body-switching incident - It Makes Sense in Context. The episode ends with him repeating 'NOBODY MUST REMEMBER!' and shooting it into the camera.
Computer game Hidden Agenda challenged you to assume the presidency of a troubled Banana Republic. The opening animation showed an assassin aiming his gun, ending on a freezeframe of him about to shoot the camera.