In the 18th century, Charleston, South Carolina, experienced a series of fires that prompted the city to pass laws requiring buildings to be constructed of fire-proof masonry, such as stone or brick. As a result, plantations with access to brickmaking materials began making brick, using the labor of enslaved people. Boone Hall Plantation, north of Charleston, was one of the largest and produced over 24 million bricks during its heyday from 1850 to 1860. Portable X-ray fluorescence spectrometry reveals the chemical fingerprint of Boone Hall bricks, and the method is tested here as a way to understand the architectural history of Boone Hall’s structures. The results can be applied throughout the region by providing a database for identifying the source of brick in Charleston structures. Brick sourcing provides a powerful personal connection between Charleston’s famous architecture and the enslaved people whose skilled labor made those buildings possible.