The Pocatalico River, a tributary of the Kanawha River, has its mouth at Raymond City in Putnam County, near Poca, at an elevation of 582 feet. Pocatalico is supposed to have been an Indian name and is reported in various spellings from the time of early European-American settlement in the region. The towns of Poca and Pocatalico, and Pocatalico Creek, are in turn named for the river. In local usage the Pocatalico is often referred to as the Poca River, and one record from as early as 1808 identifies it as the "Poky."

Coal was discovered on the Pocatalico in 1798, and mines operated in the Raymond City area for several decades prior to World War II. Extensive timbering was done along the river, beginning about 1895.

From its headwaters near Looneyville, the Pocatalico River passes in a southwestward direction through Roane, Kanawha, and Putnam counties. Its watershed includes the southern corner of Jackson County, as well. The length of the Pocatalico is 67.7 miles, and its course is very crooked. The main tributaries are Manila, Heizer, Frog, Pocatalico, and Johnson creeks, and Rocky, Legg, Middle, and Flat forks.

The Pocatalico River sweeps in an arc north of Charleston. Its drainage area includes some of the capital city's outlying suburbs, although Pocatalico's people more commonly live in the rural countryside. The river's watershed lies across the historic road from Charleston to Ripley and Parkersburg, the same general route now followed by Interstate 77. Walton, Sissonville, Pocatalico, and Poca are located on or near the Pocatalico River, and there are numerous smaller communities.