The resistant remains of salvinialean microspore massulae and megaspores have been analyzed using scanning and transmission electron microscopy and Curie-point pyrolysis. The results show a selective enrichment of specific tissues in the fossil samples. The resistant compound, sporopollenin, in these fossil remains, is shown to consist of an oxygenated aromatic, and an aliphatic moiety. The latter is selectively enriched during diagenesis and upon oxidation. The organic matter of the extant samples is dominated by compounds which, during diagenesis, are selectively removed. The morphologically distinct megaspores and microspores are chemically comparable. Furthermore, although the genera studied are strongly distinctive in morphology and ultrastructure, the variation in their chemistry is too small to use for chemotaxonomy.