Pregnane oligoglycoside, namely roylinine, and a pregnane derivative, namely marsgenin, have been isolated from chloroform-soluble extract of dried stem of Marsdenia roylei, and their structures were determined using ¹H-NMR, ¹³C-NMR, ¹H-¹H COSY, HSQC, TOCSY and FABMS spectral techniques as well as chemical degradation and derivatisation.