Governor Jerry Brown, in a statement yesterday, said he consulted members of the Catholic Church, which is opposed to measure, as well as physicians, before making the decision.
"In the end, I was left to reflect on what I would want in the face of my own death," said the 77-year-old governor, who as a young man studied to enter the priesthood.
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"I am certain, however, that it would be a comfort to be able to consider the options afforded by this bill," he added.
"And I wouldn't deny that right to others."
The bill makes California the fifth US state to allow assisted suicide after Montana, Oregon, Washington and Vermont.
A New Mexico judge in 2014 approved assisted suicide, but his decision was later struck down by an appeals court.
Euthanasia has long been a controversial issue in the United States.
The topic was brought to the forefront in California by the case of Brittany Maynard, a 29-year-old with a brain tumor who moved from San Francisco to Oregon and took her own life last November.
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