This article explores the relationship between science and empire, through the prism of British botanical engagement with the South Atlantic in the late eighteenth and early nineteenth centuries. It investigates the logistics of plant exchanges, as information, expertise, and specimens followed the maritime contours of the British empire. The discussion traces the nascent network-building undertaken by officials, residents, and visitors on St Helena and at the Cape of Good Hope, and the exchange of plant specimens with London and, crucially, with other places around the empire. The article suggests that such activities offer perspectives on wider patterns of interaction with an area located at the crossroads of Britain’s maritime empire. In time, the region forged its own botanical networks and created alternative axes of exchange, association, and movement.