re: Was the Starbucks cup actually a product placement?

Yes. shite happens. The primary and secondary focus of that scene is to the left and upper portions of the screen and an actor’s head obstructs the cup at the beginning of the shot. I’m not sure why having the ability to digitally edit it out would mean it’s on purpose. They can edit out or add anything they want in post.

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Are we really supposed to believe that it went totally unnoticed until the viewing audience immediately saw it, and then they were like “wow, we should fix that!”

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1) The viewing audience didn't see it. YOU didn't see it until it became a meme. A select few people glanced at the table instead of the Dragon Queen's reaction shot (which was the focus of the shot).

2) It did go totally unnoticed by the production team and HBO. For all that you know, that reaction shot was dropped in towards the end of the editing process for that episode. Someone doesn't like the shot they had, tells the editor to drop in a different take, boom - coffee cup.