The Coal River, which joins the Kanawha River at St. Albans, forks into two large tributaries 19 miles above its mouth. The main or east branch, the Big Coal River, itself forks about 40 miles farther upstream into its major tributaries, Marsh and Clear forks. The river's west branch, known as the Little Coal, extends southward for about 20 miles to Madison, where it splits into its main tributaries, Spruce and Pond forks. Well-named, the Coal River system drains a large section of the southern coalfields.

Most likely, the Coal River was discovered by John Peter Salling in 1742, and named by him for the coal outcroppings he saw in the area. Alternatively, the river may have been named for himself by Samuel Cole, one of a group returning from Andrew Lewis's ill-fated Sandy Creek Expedition in 1756.

The triangular-shaped Coal River basin covers about 900 square miles, including almost all of Boone County and parts of Kanawha, Raleigh, Lincoln, Logan, and Putnam counties. The watershed is roughly 20 miles wide at its broadest and about 50 miles long at its longest. From St. Albans, about 13 miles west of Charleston, the Coal and its tributaries extend southeast to the Beckley area and south toward Logan. The Coal River basin was richly endowed with natural resources, especially coal and timber. In the 1850s, the Coal River Navigation Company built eight locks and dams on the Coal as far as Peytona, to ship bargeloads of high-quality cannel coal, which was used to make coal oil. Millions of bushels of cannel coal were removed from 1867 to 1881. Later, the river was used to float logs to St. Albans sawmills, and in 1889 cribs and booms were strategically located to direct the logs into the river's main channel. By 1905, the railroad had taken over the removal of timber from the Coal River region. As the woods were timbered out and logging declined, bituminous coal mining quickly replaced it. Today, railroads extend to the tributaries of both branches, and coal production from the area remains high.

In the early 20th century the Coal River was used extensively for recreation. Two river beaches, one at Upper Falls and one at Lower Falls, remained popular for much of the century. However, coal mine pollution increasingly interfered with enjoyment of the river by bathers. As coalfield streams were cleaned up late in the century, the Coal became popular with canoeists and fishermen. Begun in 2004, the Tour De Coal is an annual event held around West Virginia Day that brings thousands of kayakers and canoeists to make the 11-mile trip from Tornado to St. Albans. Today, the Coal River Water Trail offers a number of convenient public access and launch sites.