The phytochemical investigation on the leaves of Craibiodendron yunnanense W.W. Smith resulted in the isolation of 21 compounds, including 11 known ursane triterpenes, 8 oleanane triterpenes, and 2 sterols. Their structures were clarified by analyses of their NMR spectroscopic data as well as by comparison of these data with those published in the literature. From the present investigation, compounds 1–2, 6, 8–10, 13–16, 18 and 21 were isolated for the first time from the family Ericaceae, and their chemotaxonomic significance was discussed. Additionally, compounds 21 exhibited in vitro cytotoxicity against human MDA-MB-231 and BT-549 cancer cell lines with IC50 value of 14.19 μM and 21.45 μM, respectively.