Maria and Luke appear briefly in "Cartman Finds Love." Acorrding to Stan, they got together "because they got locked in the school gym overnight." implying that Cartman locked them in the gym to get them together.
Maria and Luke are stated to be boyfriend and girlfriend because Cartman locked them in the gym overnight a few months before the events in "Cartman Finds Love".
Seeing Luke and Maria are only briefly mentioned and shown once, the couple is very unpopular and the only fanfiction involving this pairing was deleted.
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