Oxalis wulingensis, an unusual new species of Oxalidaceae from Hunan and Hubei provinces of central China, is described and illustrated. Placement of this species within Oxalis was assessed based on DNA analyses of the nuclear internal transcribed spacer (ITS) and morphological comparisons with related species. This new species can be easily distinguished by its long, obtriangular leaflets, the two lateral ones arranged at a 180° angle and densely pubescent with brown, villous hairs on both surfaces, pink flowers with lilac veins, and apex of petals obtuse or irregularly denticulate with 3–5 teeth. The chromosome number is 2n = 22. With the addition of O. wulingensis, which is the only species endemic to China, a total of seven native Oxalis occur in the country. A taxonomic key to all Chinese species of Oxalis is also provided.