Sterols and fatty acids composition of some members of green algae were analysed as tools for chemotaxonomy. Nearly from the orders of green algae, at least a representative member was chosen as a basic model for the order. Some bryophytan members were also studied for convenience. Owing to the debatable systematic position of Vaucheria it was also chosen and analysed together with the members of Chlorophyta. The data obtained suggested an obvious relation between members of Chara and chlorophytes rather than between members of Chara andbryophytes. Members of Chara might be therefore considered to be green algae under a separate order ^“Charales", at the top of the orders in the green algae of the division of Chlorophyta. The results stand strongly against the idea that members of charophytes must be elevated to the rank of class or phyla. The data proved also that the sequence of the top three orders in Chlorophyta must be arranged as follows: Conjugales, Siphonales & Charales. Finally Vaucheria was found to be distant from Chlorophyta.