Biochemical studies have complemented ultrastructural and, subsequently, molecular genetic evidence consistent with the Charophyceae being the closest extant algal relatives of the embryophytes. Among the genes used in such molecular phylogenetic studies is that (rbcL) for the large subunit of ribulose bisphosphate carboxylase–oxygenase (RUBISCO). The RUBISCO of the embryophytes is derived, via the Chlorophyta, from that of the cyanobacteria. This clade of the molecular phylogeny of RUBISCO shows a range of kinetic characteristics, especially of CO2affinities and of CO2/ O2selectivities. The range of these kinetic values within the bryophytes is no greater than in the rest of the embryophytes; this has implications for the evolution of the embryophytes in the high atmospheric CO2environment of the late Lower Palaeozoic. The differences in biochemistry between charophycean algae and embryophytes can to some extent be related functionally to the structure and physiology of embryophytes. Examples of components of embryophytes, which are qualitatively or quantitatively different from those of charophytes, are the water repellent/water resistant extracellular lipids, the rigid phenolic polymers functional in waterconducting elements and mechanical support in air, and in UV–B absorption, flavonoid phenolics involved in UV–B absorption and in interactions with other organisms, and the greater emphasis on lowMrorganic acids, retained in the plant as free acids or salts, or secreted to the rhizosphere. The roles of these components are discussed in relation to the environmental conditions at the time of evolution of the terrestrial embryophytes. A significant point about embryophytes is the predominance of nitrogen–free extracellular structural material (a trait shared by most algae) and UV–B screening components, by contrast with analogous components in many other organisms. An important question, which has thus far been incompletely addressed, is the extent to which the absence from bryophytes of the biochemical pathways which produce components found only in tracheophytes is the result of evolutionary loss of these functions.