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James VI of Scotland, son of Mary, Queen of Scots, became King James I of England upon the death of Elizabeth I because he was her closest living relative. James was related to Elizabeth through her aunt, Henry VIII's sister, Margaret Tudor. Margaret was James' great-great grandmother and as Elizabeth had no children, he was the next in line for the English throne. With James' succession, began the House of Stuart.

Margaret Tudor, Henry VIII's sister, married James IV of Scotland who begat James V, who married Marie de Guise from France, and begat Mary, Queen of Scots, the mother of James VI, who eventually became James I of England.

http://en.wikipedia.org/wiki/James_I_of_England#Proclaimed_King_of_England

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