To the white South in 1861 , it was an article of faith that the Civil War -- or the War of the Rebellion, as it was most commonly known in the North -- could have been avoided had Abraham Lincoln allowed the seven states of the lower South to secede peacefully. To many today, this remains an article of faith. And in fact Lincoln's call for 75,000 volunteers (partly in response to the South's call for 100,000 soldiers) and subsequent order to blockade southern served as the flashpoint for the secession of Virginia, Tennessee, North Carolina, and Arkansas.
But was there ever a chance for peaceful secession?
Doubtful.
The immediate problem with the peaceful secession argument is obvious: If prevention of civil war was the paramount concern (and it wasn't), then the seceding states could have just as easily prevented it by honoring the legitimacy of the democratic process and not seceding. More to the point, though, peaceful secession would not have addressed the underlying cause of the Civil War.
In 1861, the white South had a much greater commitment to the moral legitimacy of slavery (and white supremacy) than the North had to its abolition. The North opposed the expansion of slavery into the western territories on economic grounds: That free labor could not possibly compete with slave labor, and that permitting slavery in the territories was tantamount to establishing it as the economic basis for expansion.
That being said, neither side thought that slavery would survive unless it was allowed to expand its geographic reach. (I'm using "side", "North," and "South" loosely, as clearly views in each region were diverse and nuanced.) Popular sovereignty compromises had proved counterproductive, and fighting had already broken out in territories over this question independently of secession.
Thus, the white South's contention that limiting slavery to where it was in place amounted to abolishing it was basically correct. But -- even under peaceful secession -- the North would never have permitted the extension of slavery and would have opposed it with force. Essentially, that's what it did, except that it took the fight (primarily) to the slaveholding states instead of the territories.
At the same time, the white South -- considering its position at the time -- would have resisted any northern attempt to squelch the extension of slavery. Essentially, that's what it did.
And so, as Lincoln said, the war came. He tap-danced around the true cause when he added that slavery was "somehow the cause of the war." The nation began down the bloody path when it permitted slavery in a society in which all men were supposed to be created equal. It is an irony that the explosion came over the threat of slavery to equal economic opportunity for whites.