The phytochemical investigation of the roots of Euphorbia bupleuroides Desf. (Euphorbiaceae) yielded three new compounds named 4,20-dideoxy(4a)phorbol-12-benzoate-13-isobutyrate (1), 25-hydroperoxycycloart-3b-ol (2), and 3b,7b-dihydroxy-4a,14a-dimethyl-8b,9b-epoxy-5a-ergosta-24(28)-ene (3), together with 17 known compounds 4–20. Their structures were established from analysis of 1D (¹H, ¹³C and DEPT) and 2D NMR (COSY, HSQC, HMBC and NOESY) data, and of mass spectrometry (HRESIMS), and by comparison with literature data.