An expression used when talking about a girl who has dyed her hair

If it's not directly obvious the phrase comes from the wearing of a coat with furry collar and cuffs, the indication being that the collar and cuffs don't match in colour in much the same way as the hair on her head doesn't match the hair on her genitals.

Commonly used in sentences such as "Nice tits, pity she's not collar and cuffs"

Actually, this one comes from menswear. From the early nineteenth century until after World War II, men widely wore highly starched, detachable collars and, to a lesser extent, detachable cuffs. It was initially a practical decision--why wash the whole shirt when only the neck and hands get dirty? Of course, nothing says "I have enough money to afford laundering, and thus have social standing" like a four-inch gleaming white collar amid sooty Victorian England. To this day, shirts with a colored or patterned body and solid white collar (and often a matching French cuff) are moderately popular.

James Bond fans will recall this exchange from Diamonds are Forever:

Bond: Weren't you a blonde when I came in?
Tiffany Case: Could be.
Bond: I tend to notice little things like that - whether a girl is a blonde or a brunette.
Tiffany Case: Which do you prefer?
Bond: Well, as long as the collar and cuffs match...

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