Pickens was born in Togadoo, St Paul's Parish, in Colleton County, South Carolina.

He joined the Democratic Party and served in the South Carolina house of representatives from 1832 to 1834, where he was an ardent supporter of nullification.

As chairman of a sub-committee, he submitted a report denying the right of Congress to exercise any control over the states.

Under President James Buchanan, Pickens was Minister to Russia from 1858 to 1860, where he and his wife were befriended by Czar Alexander II.

Under his administration as Governor of South Carolina (1860–1862), the state seceded and demanded the surrender of the Federal forts in Charleston harbor.

[7] On January 9, 1861, Governor Pickens sanctioned the firing upon the relief steamship Star of the West, which was bringing supplies to Anderson's beleaguered garrison.

[6] In a letter dated January 12, 1861, Pickens demanded of President Buchanan that he surrender Fort Sumter because "I regard that possession is not consistent with the dignity or safety of the State of South Carolina.

Pickens was a member of the South Carolina constitutional convention called in September 1865 shortly after the end of the Civil War.

"[9] According to the New York Times: "The passage was received in silence – strikingly suggestive when one remembered with what dramatic applause the ordinance of secession was proclaimed passed.

"It doesn't become South Carolina to vapor or swell or strut or brag or bluster or threat or swagger," Pickens said. "