Most unusual/mesmerizing female voice.

Natalie Merchant gets my #1 vote!
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I'm going with Bjork. Love that voice!
Forgot the Queen...

Mary Fahl (formerly of October Project)
One of my favorite, Brandi Carlile. and let not forget the late Eva Cassidy.
No one has mentioned Lisa Gerard (Dead Can Dance).
Alison Moyet, Yaz and solo...