Oakville started life in the 1860s as a water stop for the steam train owned by The Napa Valley Railroad Company.

The railroad, founded by early California pioneer Samuel Brannan in 1864, shuttled tourists between ferry boats that docked in Vallejo to the resort town of Calistoga.

The village gained its name from the dense groves of dark green valley oaks of the area.

Formally declared a Napa appellation in 1993 there are currently 24 wineries and over 5,000 acres (20 km2) of vineyard located within the boundary of the Oakville AVA.

The Robert Mondavi Winery is located between Oakville and Rutherford, California (though its corporate headquarters are in nearby St. Helena).

Modern day tourists traveling on State Route 29 often include a stop at Oakville Grocery, one of the area's few non-winery business, in order to purchase picnic supplies.

According to the United States Census Bureau, the CDP covers an area of 1.4 square miles (3.5 km2), all of it land.

On the Napa County Board of Supervisors Oakville is in District 3 and is represented by Diane Dillon.