This phrase is uttered by a person who asks a lot of questions because they are curious.
Tina: "Rory! Why do you ask me so many questions ?!?!?"
Rory: "I don't know, Tina. I guess I'm just really curious . . . Call me George!"
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Kinda like "Ill be dammed" just funnier
Guy 1:"Dude it worked!"
Guy 2:"Well fuck me sideways and call me George"
Guy 1:"Wait, what?"