An inventory of the botanical resources of Doe Mountain Recreation Area, comprising 3480 ha on the boundary of the Blue Ridge and Ridge and Valley ecoregions in extreme northeastern Tennessee, was conducted to help guide conservation-based management. A total of 486 species (including subspecies and varieties) was found comprising 95 families, 286 genera, 11 species tracked on the state rare plant list, 153 county records, and 77 exotic species. The relatively high ratio of county records to exotics indicated an area of conservation merit, but the ratio was lower than in floras from comparable areas in eastern Tennessee. The vast majority of county records were of common species, suggestive of an under-collected county. However, some of the noteworthy county records and state-listed species were from unusual habitats such as acid seeps, wetlands, and xeric ridges. Two species, Liatris virgata and Lycopodiella inundata, were new to the state. Water in the seep that supports L. inundata was an order of magnitude more acidic (pH=3.56) than at other sites. An analysis of the wildland–urban interface showed that the periphery of the site had more human impact than the county as a whole with the highest impact on the northern half; only 13% of the area was classified as uninhabited. Management recommendations, some of which were already adopted, targeted protection of acid seeps and xeric roadside slopes, curtailing mowing and herbicide use near a wetland that supports a state endangered species, and reconnaissance for exotic invasions in a biodiverse power line corridor.