Dona Catherina of Ceylon, Black Widow Serial Killer - 1613

She poisoned her husband, Mahatissa, surnamed The Robber [Cora-Niiga, or Niiga the rebel, or robber], and ascended the throne. In the course of five years she married and killed five husbands and was finally put to death by her step-son. Donna Catherina is not acknowledged as a queen by the Sinhalese chroniclers. 

[Bella Sidney Woolf, How to see Ceylon, The Times of Ceylon Co. Ltd., 1924, p. 27]

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For links to other cases of woman who murdered 2 or more husbands (or paramours), see Black Widow Serial Killers.

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