Zollicoffer attended the local schools and studied for a year at Jackson College in Columbia, Tennessee. He left at the age of sixteen, became an apprentice printer, and was engaged in newspaper work in Paris, Tennessee, from 1828 to 1830. When the newspaper closed, he moved to Knoxville in 1831 and worked for two years as a journeyman printer at the "Knoxville Register". Three years later, he became editor and part owner of the "Columbia Observer". Zollicoffer was elected State Printer of Tennessee in 1835.