The progress achieved in the development of fluorocarbon-based blood substitutes since the advent of Fluosol-DA is summarized. Special emphasis is placed on the synthesis and evaluation of more adequate, reliable, industrially feasible fluorocarbons, structure/property relationships. The preparation of significantly more concentrated, more efficacious emulsions, etc. The key to further progress and better mastery of the emulsions' characteristics, especially in relation to increased shelf life, prolonged intravenous persistence, and versatility, now lies in the development of new surfactants, better adapted to this objective. New families of well-defined, monodisperse perfluoroalkylated polyhydroxylated surfactants derived from sugars and related compounds have been synthesized and fully characterized. Preliminary evaluation of their surface-active properties, emulsion-stabilizing capacity and biocompatibility are reported.