Zollicoffer was born in Maury County, Tennessee, to John Jacob Zollicoffer and Parthenia (Carter) Zollicoffer in 1812. He attended Nashville Academy, where he studied law. After completing his studies, Zollicoffer moved to Paris, Tennessee, where he practiced law and became involved in politics.
In 1841, Zollicoffer was elected to the Tennessee House of Representatives, where he served for two terms. In 1843, he was elected to the United States House of Representatives, where he served for one term. During his time in Congress, Zollicoffer supported the annexation of Texas and the expansion of slavery into the western territories.
After leaving Congress, Zollicoffer returned to Tennessee and continued to practice law. He also became involved in the Whig Party and was elected to the state legislature in 1847. In 1849, he was appointed state comptroller.
When the Civil War broke out in 1861, Zollicoffer joined the Confederate Army and was appointed a brigadier general. He was assigned to command the Department of East Tennessee and was tasked with defending the region against Union forces.
In November 1861, Zollicoffer's forces clashed with Union forces at the Battle of Camp Wildcat. The battle was a Confederate defeat, but Zollicoffer was killed in action.
Zollicoffer was a respected soldier and politician. He was a strong supporter of slavery and the Confederacy, and he was willing to fight for his beliefs.