On May 25th, 1749, the Virginia General Assembly passed the act that separated Chesterfield from Henrico County and created the new county. The county is named for Philip Stanhope, 4th Earl of Chesterfield. Lord Chesterfield was famous for his "good manners and writings."

In 1831, the Chesterfield Railroad was the first railroad in Virginia, transporting coal from mines near Falling Creek in what is now the Midlothian area to the docks at the fall line at the head of navigation of the James River near Manchester (directly across from Richmond. Manchester was the county seat until 1874.

Chesterfield Cigarettes were named after this county due to the region's historical association with the tobacco industry.

As of the census of 2000, there are 259,903 people, 93,772 households, and 72,110 families residing in the county. There are 93,772 households out of which 40.70% have children under the age of 18 living with them, 62.20% are married couples living together, 11.20% have a female householder with no husband present, and 23.10% are non-families. 18.50% of all households are made up of individuals and 4.80% have someone living alone who is 65 years of age or older. The average household size is 2.73 and the average family size is 3.11.