Whiteville is located in northwestern Hardeman County at  U.S. Route 64 runs through the southern part of the town, leading southeast 11 miles (18 km) to Bolivar, the county seat, and southwest 13 miles (21 km) to Somerville. Tennessee State Route 100 runs east from Whiteville 30 miles (48 km) to Henderson. State Route 179 runs north from the center of Whiteville 15 miles (24 km) to Interstate 40 at Willis.(35.324496, -89.145721).
According to the United States Census Bureau, Whiteville has a total area of 2.7 square miles (7.1 km2), all land. The town is drained by the headwaters of Hickory Creek, which flows north to the Hatchie River.
As of the census of 2000, there were 3,148 people, 457 households, and 308 families residing in the town. The population density was 1,317.7 people per square mile (508.6/km²). There were 510 housing units at an average density of 213.5 per square mile (82.4/km²). The racial makeup of the town was 38.02% White, 60.93% African American, 0.10% Native American, 0.06% Asian, 0.13% from other races, and 0.76% from two or more races. Hispanic or Latino of any race were 0.76% of the population.
There were 457 households out of which 29.5% had children under the age of 18 living with them, 37.4% were married couples living together, 26.5% had a female householder with no husband present, and 32.4% were non-families. 29.3% of all households were made up of individuals and 16.0% had someone living alone who was 65 years of age or older. The average household size was 2.53 and the average family size was 3.12.
In the town, the population was spread out with 10.5% under the age of 18, 16.9% from 18 to 24, 51.4% from 25 to 44, 14.3% from 45 to 64, and 6.9% who were 65 years of age or older. The median age was 32 years. For every 100 females there were 387.3 males. For every 100 females age 18 and over, there were 483.4 males.
The median income for a household in the town was $22,368, and the median income for a family was $28,603. Males had a median income of $22,050 versus $19,013 for females. The per capita income for the town was $11,310. About 21.0% of families and 18.7% of the population were below the poverty line, including 18.4% of those under age 18 and 20.6% of those age 65 or over.
Tennessee Colleges of Applied Technology has a location in Whiteville.