Bluefield, incorporated in 1889, embodied the rapid growth of the southern West Virginia "smokeless" coalfields. Located in a broad valley between the headwaters of the Bluestone and East rivers along the Virginia border, the site was for 100 years the homestead of the Bailey and Davidson families. The decision of the Norfolk & Western Railway (N&W) to locate its Pocahontas Division headquarters there in 1882 created the modern community. The N&W's natural gravity switching system made the Bluefield yards a model of efficiency and productivity. Around the railroad's offices, rail yard, and shops gathered banks, utilities, and the wholesale warehouses that stocked coal company stores in the booming Pocahontas Coalfield.

By 1910, Bluefield's population exceeded 10,000. Stately Federal Revival buildings in the downtown commercial district began to climb the hill southward toward East River Mountain, on whose slopes grew blue fields of chicory, the town's namesake. Bluefield's progressive 1921 city charter made it just the second city in the nation to adopt the city manager form of local government. By 1950, about 25,000 people lived in Bluefield, inducing adjoining Graham, Virginia, to change its name to Bluefield, Virginia. The 12-story West Virginian Hotel is the tallest building in West Virginia south of Charleston.

Bluefield's political Kee family—John, Jim, and Elizabeth—held West Virginia's Fifth Congressional District seat in Washington for 40 years. Hugh I. Shott built the Bluefield Daily Telegraph into a powerful media empire, and his WHIS radio, which began broadcasting in 1929, was an important leader in the early history of country music. Bluefield State University, a member of the state public college system, was founded in 1895 as Bluefield Colored Institute, and stands as evidence of the community's rich heritage of diversity. Mechanization of the coal industry and transportation changes, however, began inexorably to erode Bluefield's position of regional leadership. The city’s population declined from a peak of 21,506 in 1950 to 9,658 in 2020.

Bluefield remains the largest city in Mercer County. Bluefield is known as "Nature's Air-Conditioned City," and civic officials distribute free lemonade on the infrequent days when the temperature exceeds 90 degrees. Both the South Bluefield residential neighborhood district and the central business district are listed in the National Register of Historic Places.