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This is a tricky question. The first king and queen ever or of a particular land? I personally choose to talk about the Egyptian people who exalted Pharaohs as their rulers. Please see the notes section as to why I chose the Egyptians.
The Pharaoh I see as the first "King" was named Narmer (Horus Nameru). While there are pharaohs previous to Narmer (ex. Ka, Wazner, Thesh, etc...) it is held to be Narmer who united the Upper and Lower Egypt into the "kingdom" of Egypt. According to the Great Hierakonpolis Palette Narmer was ruling during 3100 B.C.
His "queen" is thought to be Neithhotep. She is believed to have been a princess of the Upper Egypt region.
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