The oxidised derivatives of phytosterols (oxyphytosterols) were identified in plasma samples from thirteen healthy human volunteers, using MS. All the samples contained noticeable quantities of (24R)-5β,6β-epoxy-24-ethylcholestan-3β-ol (β-epoxysitostanol) and (24R)-ethylcholestan-3β,5α,6β-triol (sitostanetriol) and also trace levels of (24R)-5α,6α-epoxy-24-ethylcholestan-3β-ol (α-epoxysitostanol), (24R)-methylcholestan-3β,5α,6β-triol (campestanetriol) and (24R)-ethylch olest-5-en-3β-ol-7-one(7-ketositosterol). The amounts of these oxyphytosterols in plasma varied from 4·8 to 57·2 ng/ml. There are two possibilities concerning the origin of these compounds. First, they could come from the small amounts of oxyphytosterols in food. Second, they could originate from the in vivo oxidation of phytosterols in plasma. Very few data actually exist concerning these compounds. Their identification in human samples suggests that further research is necessary in this field.