With an abundance of iron ore, timber for charcoal, limestone for flux, and water power, it is not surprising that iron making was one of Western Virginia's earliest industries. Iron making began in present Jefferson County in 1742, when the Quaker William Vestal erected Vestal's Bloomery near the Shenandoah River. Bloomeries such as his served an important role on the frontier, producing small batches of wrought iron, a commodity needed for the manufacture of nails, tools, and agricultural implements. Other bloomeries were subsequently established, including one at Bloomery, Hampshire County, in the early 1760s. Several bloomeries were likely constructed along the tributaries of the South Branch of the Potomac near Moorefield in the early 1790s.

Gradually, blast furnaces and forges appeared. Furnaces and forges had a much greater output than the bloomeries and enabled the local manufacture of skillets, pots, salt pans and kettles, and other cast-iron goods, as well as bar iron, nails, and other wrought-iron products. John Semple, a Bladensburg, Maryland, entrepreneur, constructed West Virginia's first blast furnace, the Keep Tryst Furnace, along the Potomac River in present Jefferson County in 1763. Keep Tryst initiated a new era, but the American Revolution interrupted the westward expansion of the iron industry, and several decades passed before it crossed the mountains. The completion of the short-lived Peter Tarr Furnace, about 1794 in present Hancock County, signaled the start of post-Revolution iron production in northwestern Virginia.

Another iron making region emerged in present north-central West Virginia, where about 1798 Samuel Hanway established the Rock Forge on Deckers Creek near Morgantown. Samuel Jackson, a Pennsylvania Quaker, established Jackson's Ironworks about 1809 at Ices Ferry on the Cheat River in Monongalia County. It grew in succeeding decades to become one of the state's leading antebellum ironworks. The local iron industry (also called Cheat Mountain iron industry) continued to mature, reaching its peak in the late 1850s. Still another iron making region developed in Hardy and Hampshire counties (including present Grant and Mineral counties), where the earliest furnaces were put in operation about 1800. This region's most significant and enduring iron making concern was the Capon Iron Works, built by James Sterrett about 1832. Located near Wardensville, this ironworks operated into the 1880s.

By 1860, 28 charcoal iron furnaces had been constructed in 11 Western Virginia counties. These counties formed a crescent from Jefferson County to Hancock County, with Monroe being the single outlying exception. By the Civil War, the majority of Western Virginia's iron makers had ceased production. This was primarily due to the general lack of transportation improvements in Western Virginia, which prohibited iron products getting to the larger markets, and to a lesser extent to the competition of inexpensive anthracite iron from eastern Pennsylvania. Following the Civil War, newly created West Virginia's charcoal iron industry experienced a short-lived rebirth. But this technology was now virtually obsolete with the industry's adoption of coke fuel, and these furnaces ceased production by the early 1880s.

West Virginia's modern iron making era began in the New River Gorge at Quinnimont. There in 1874, investors hoping to create the "Pittsburgh of the South" erected a coke-fueled blast furnace along the recently completed Chesapeake & Ohio Railway. The furnace used coke made from New River coal and iron ore from Alleghany County, Virginia. Transporting iron ore a great distance was an unusual practice, and it caused the furnace to fail repeatedly, ultimately closing for good in 1884.

During this same period, the Northern Panhandle emerged as the modern center of coke-based iron and steel making in West Virginia. Wheeling's first ironworks, Top Mill, was established about 1834 by Pittsburgh iron masters. By 1860, there were at least four Wheeling ironworks that produced cut nails, a very important 19th-century commodity. In the early 1870s, Wheeling nail makers integrated their manufacturing operations, first constructing modern coke-fueled blast furnaces and then in the early 1880s added steel making facilities. Wheeling nail makers survived the decline of the cut nail industry by diversifying the product line to include welded-steel pipe (a Wheeling first in 1882), sheet steel, steel slabs, and other semi-finished steel products. In 1920, the last three independent Wheeling steelmakers, the La Belle Iron Works, the Wheeling Steel & Iron Company, and the Whitaker-Glessner Company, merged to form the Wheeling Steel Corporation, which became the Wheeling-Pittsburgh Steel Corporation in 1968. After a number of acquisitions, Wheeling-Pittsburgh Steel closed in 2013. The old La Belle cut nail factory closed in 2015. Cleveland-Cliffs eventually acquired Wheeling-Pittsburgh’s old coke-making facility in Follansbee and closed it in 2022.

The manufacture of tin plate, needed for tin cans, resulted in the formation of West Virginia's other major iron and steel producer, the Weirton Steel Corporation. In 1890, Congress enacted the McKinley Tariff to stimulate the domestic production of tin plate, and subsequently tin plate mills were established at Wheeling, Morgantown, Chester, and Clarksburg. In 1905, Earnest T. Weir purchased the Jackson Iron & Tin Company tin mill located at Clarksburg, and by 1909, had relocated his mill to Hollidays Cove in Hancock County. The company thrived, resulting in the formation of the Weirton Steel Corporation in 1918. After a decade, Weirton Steel in 1929 merged with Michigan Steel of Detroit and M. A. Hanna Steel of Cleveland to form National Steel Corporation. In 1982, under an Employee Stock Ownership Plan (ESOP), the Weirton workers purchased the plant from National Steel Corporation. After a period of bankruptcy Weirton Steel ceased to be an employee-owned company in 2004, when it was sold to International Steel Group of Ohio. The former Weirton Steel was last owned by Cleveland-Cliffs, which announced in 2024 the shuttering of its remaining Weirton operations.

West Virginia's remaining steel production has declined significantly in the 21st century due largely to competition from underpriced imported products. As of the 2020s, a few manufacturers still exist but not on the scale of the past. Constellium in Ravenswood; Huntington Steel, Steel Dynamics, and Steel of West Virginia, all in Huntington; and Precision Stamping in South Charleston, are among the larger operations. The state is banking on new multibillion-dollar projects, such as ones proposed by Nucor West Virginia in Apple Grove, Mason County; Commercial Metals in Berkeley County; and Form Energy's battery manufacturing plant on part of the former Weirton Steel site.