Paphiopedilum motuoense, a newly discovered orchid from Motuo County, Xizang, China, is described and illustrated. Paphiopedilum motuoense can be distinguished from the related Paphiopedilum species P. qingyongii and P. venustum by several distinctive features: a significantly smaller staminode above the column, a distinct purplish-red lip with purplish-brown veins, pouched with erect and triangular auriculas on both sides of its mouth, and leaves with pale green and pale yellowish-green tessellations. The novelty is also well supported as a new species by molecular phylogenetic analysis. Additionally, the complete chloroplast genome of P. motuoense, 157,218 bp in length, was assembled and annotated. It contains an LSC region of 86,275 bp, SSC region of 949 bp and two IRs of 34,997 bp, with 120 genes, including 76 PCGs, 36 tRNA genes and 8 rRNA genes.