Pocahontas has a long history dating back to the 1700's when the region was occupied by the French and a number of Indian tribes, including the Osage and Cherokee. The city's first settler, Ransom S. Bettis, arrived from Greenville, Missouri, in the early 1800's and is credited with helping establish Pocahontas as the county seat.

Pocahontas began as a significant river port and the first supply stop in Arkansas for travelers coming down Old Southwest Road. Several famous frontiersmen, including Sam Houston, Stephen F. Austin, General Ulysses S. Grant and others, made stops in Pocahontas during this time. Even today, the city continues to serve as a strategic educational and agricultural center for Randolph County and the state.

The city constructed its first courthouse in 1837, a 40 feet by 40 feet two story structure. After the courthouse collapsed in 1870, Pocahontas residents replaced the structure in 1875 with the historic courthouse that remains today. The courthouse is a central landmark in Pocahontas' historic downtown business square with most of the commercial outlets renovated to compliment the building.

Pocahontas served as a major recruiting, training, and supply center during the Civil War. The city housed as many as 10,000 men after Arkansas withdrew from the Union on May 6, 1861. These men helped the state prepare for combat and secure the northern border from invasion. Federal troops even burned a section of the city, including the Pocahontas newspaper office, during the conflict.

The late nineteenth century through the mid-1920s marked a golden age for Pocahontas. The city had seven hotels and forty-three steamboats that navigated the Black River and turned Pocahontas into an important port of commerce. During this time, Pocahontas landed the Hoxie, Pocahontas, and Northern Railroad in 1896, completed the Hauk Railroading Company's connection of Poplar Bluff, Missouri, to Pocahontas in 1902, and watched the San Francisco Railroad construct a new railroad bridge across the Black River in 1911. Other early industries included four button factories, a brick company, Hanauer's cotton gin, the Grafton Stave and Heading Company, and the Pocahontas Bending Works, which made wooden parts for wagon wheels around 1901.

Development slowed during the 1920s and 1930s until several industries began to locate in the area. In 1942, Pocahontas landed a factory that made powdered eggs for the army and employed about 500 residents. Brown Shoe Company came to the area just a few years later, becoming the largest employer in Pocahontas. Other factories came in the 1960s including McGee, Aircraft Engineer, Cinch, and Pro Group, followed by Amerace ESNA in the 1970s.

Pocahontas continues to benefit today from its central location between the hills of the Ozarks to the west and the rich farmland of the Delta to the east. Tourists and residents flock to the region's five rivers year-round for all types of recreational activities including fishing and canoeing. The city is also home to the Black River Technical College which contributes significantly to the region's educated workforce.