Four new cerebrosides 4-6 were isolated from the latex of Euphorbia biglandulosa Desf. and their structures determined. Normal and reverse-phase flash chromatography was effective for the isolation of the cerebrosides, and FAB-MS spectrometry, 1H-NMR, 13C-NMR, DQF-COSY and HMQC experiments and chemical reactions were useful in elucidating their structure. EI-MS of the dimethyl disulfide derivatives of the long chain bases and glucosphingoside-heptaacetates was decisive for the determination of the double bond position on the long chain parts.