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If the bombardment of Fort Sumter was the spark that eventually led to the US Civil War, then the best answer, the most straight forward forward answer was Virginia. It seceded after President Lincoln sought 75,000 volunteers to end the rebellion in South Carolina. This sent Virginia to join the new Confederacy.

However,

it was not long after the November 1860 presidential elections that South Carolina seceded from the US. It declared itself an independent nation, for all practical purposes on December 20, 1860. It created its own army for its defense.

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