Is this sentence punctuated correctly?
Not only am I a wife, but a mother; not only a daughter, but a sister; not only a coworker, but a friend.
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No. However, the problem doesn't originate with the semicolons but with the commas. I see what you're trying to do, though. You have a series of items with their own commas, so you're using semicolons to separate them. This would be correct except the items here don't need commas.
The correct punctuation is as follows, along with the missing words. I also had to revise the first few words to solve a parallelism problem.
I am not only a wife but also a mother, not only a daughter but also a sister, not only a coworker but also a friend.
Why no commas? "Not only...but also" is a correlative pair. Correlative pairs aren't divided with commas. See "Commas with But Also": http://zencomma.wordpress.com/2011/06/18/comma-with-but-also/ for more information about correlative pairs.