The steroidal derivatives, fatty acid alkyl esters and triacylglycerols have been identified in two cultured dinoflagellates, Woloszynskia coronata and Ceratium furcoides, and natural populations of two species, Penidinium lomnickii and P. cinctum. Within each species, the same sterol moieties occurred in free and esterified forms, but the species differed in the proportion of 4.alpha.-methyl and desmethyl sterols. Both groups occurred in the two Peridinium species, whereas W. coronata contained only 4.alpha.-methylsterols and C. furcoides, uniquely among dinoflagellates analysed to date, contained only desmethylsterols, although these were analogues of 4.alpha.-methylsterols present in the other species. 4.alpha.-Methyl steroidal ketones were present in P. lomnickii and W. coronata; cholest-4-en-3-one and 5.alpha.-cholestan-3-one were detected in C. furcoides, but no steroidal ketones were detected in P. cinctum. Methyl and ethyl esters of fatty acids (C12-C18) were detected in three species, in P. cinctum the ethyl esters were dominant, while phythyl esters occurred only in the Peridinium ssp. The molecular composition of triacylglycerols containing only saturated and monoenoic acyl groups was determined by GC-MS. Lower carbon number constituents from W. coronata contained a C4 acyl group, previously found only in animal milk fats.