Ten new C21-steroidal derivatives, namely gordonosides A-L (1-10) were isolated from a chloroform extract of the aerial parts of Hoodia gordonii, a plant widely used in the nutraceutical market as an ingredient of weight loss supplements. Compounds (2-10) are based on 3beta,14beta-dihydroxy-pregn-5-en-17-betaone aglycone (1). Their structures were characterized on the basis of HR-MS spectrometry and both 1D and 2D NMR techniques.