The head was lost after revolutionaries ransacked the royal chapel at Saint Denis, near Paris, in 1793.
A head, presumed to be that of Henri IV, has passed between private collectors since then.
A team of scientists used the latest forensic techniques to identify features seen in portraits of the king.
A lesion near his nose, a pierced ear and a healed facial wound - from a previous assassination attempt - were among the marks that identified the head.
The methods used to embalm the head also matched techniques in use at the time of his death, said the scientists in a report published by the British Medical Journal (BMJ).
'Worth a Mass'It was not possible to use DNA evidence to identify the head because it was impossible to find a sample from it that could be guaranteed to be uncontaminated.
"The human head had a light brown colour, open mouth and partially closed eyes," said the scientists, led by forensic pathologist Philippe Charlier.
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