Petrocodon wui F.Wen & R.B.Zhang (Gesneriaceae), a typically lithophyte occurring in the Danxia areas of north-western Guizhou, China, is described and illustrated as new to science. The new species shows overall similarity with P. chishuiensis Z.B.Xin, F.Wen & S.B.Zhou, which is also its sister species, based on molecular evidence. The new species can be distinguished from P. chishuiensis by the elongated rhizome, the relatively long indumentum on the peduncle, the shape, size and indumentum of calyx lobes, the location of the stamens in the corolla tube and the shape, size and indumentum of the stigma. We provide a diagnosis, detailed description, photographic images and a table with taxonomic notes to distinguish several other morphologically similar Petrocodon species.