With the entry of the princes of the Nassau-Usingen and Nassau-Weilburg cadet branches to the Confederation of the Rhine in 1806, the Duchy of Nassau was formed, with Wiesbaden serving as its capital.

The annexation of the Duchy of Nassau by Prussia after the Austro-Prussian War in 1866 led to another administrative reorganization.

The duchy was included in the Prussian administrative region of Wiesbaden along with the former Free City of Frankfurt.

The collections are divided into six groups: The historical collections include: The Hessian Central State Archives has dual responsibilities: In addition to the archives from the registries of state offices and ecclesiastical institutions, the Hessian Central State Archives also holds documents of non-governmental origin, such as political parties and associations, as well as the nachlässe of scientists, people from contemporary history, and politicians.

Between 1981 and 1985, a new building was built on Mosbacher Straße in Wiesbaden, reflecting the latest in archival technology.